Process to prepare an electrode for an electrochemical storage device

Abstract

A process to prepare an electrode for an electrochemical storage device by spraying an aqueous slurry composition comprising water, xanthan gum, a source of conducting carbon particles and an active material on an electrode base. The slurry may be made by first mixing solid xanthan gum with the conducting carbon particles and the active material and secondly adding water to the resulting mixture. Alternatively the slurry is obtained by mixing solid xanthan gum with a carbon-based active material and adding water to the resulting mixture obtained.

Claims

1. A process to prepare an electrode for an electrochemical storage device comprising the following steps in the following order: (ai) mixing solid xanthan gum with a source of conducting carbon particles and, optionally the active material by shear stress; (aii) adding an active material to the resulting mixture obtained in step (ai) in case the active material was not added or not sufficiently added in step (ai); (aiii) adding water to the resulting mixture obtained in step (ai) or (aii) to form a flowable aqueous slurry composition such that the content of solids in the resulting aqueous slurry is between 2 and 25 wt. %; (aiv) spraying the flowable aqueous slurry composition consisting of water, xanthan gum, the conducting carbon particles and the active material on an electrode base to obtain a covered electrode base; (av) drying the covered electrode base; wherein an improved adhesion is obtained between the electrode base and the coating formed by the sprayed flowable aqueous slurry composition.

2. The process according to claim 1, wherein the electrode is an anode and the active material is selected in the group consisting of a carbon based material, Si—C composites, Sn—C composites, Sn or Si particles, LiTiO.sub.2 or Li.sub.4Ti.sub.5O.sub.12.

3. The process according to claim 1, wherein the electrode is a cathode and the active material is selected from the group consisting of LiCoO.sub.2, LiNiO.sub.2, LiMn.sub.2O.sub.4, LiFePO.sub.4, LiMnPO.sub.4, LiFe.sub.xMn.sub.yCO.sub.1−xPO.sub.4, LiNi.sub.xMn.sub.yCo.sub.1−x−yO.sub.2, Li.sub.1+xNi.sub.yMn.sub.zCo.sub.1−x−y−zO.sub.2, LiNi.sub.xMn.sub.yCo.sub.2Al.sub.1−x−y−zO.sub.2, Li.sub.1+xNi.sub.yMn.sub.1−xCo.sub.zO.sub.2, or Cu.sub.2ZnSn(S,Se).sub.4.

4. The process according to claim 1, wherein the electrode base is composed of a metal or carbon and/or nanotube-covered substrates.

5. The process according to claim 1, wherein in step (ai) (aii) the content of active material is between 70 and 95 wt. %, the content of solid xanthan gum is between 2 and 8 wt. % and the content of the source of conducting carbon particles is between 1 and 25 wt %.

6. The process according to claim 1, wherein in step (ai) first the solid xanthan gum is mixed with the conducting carbon particles, (aii) adding active material to the resulting mixture and (aiii) adding water to the resulting mixture obtained in step (aii).

7. The process according to claim 1, wherein in step (ai) first the solid xanthan gum is mixed with the conducting carbon particles and active material and (aiii) adding water to the resulting mixture obtained in step (ai).

8. The process according to claim 1, wherein the mixing in step (ai) is performed by planetary ball milling.

9. A process to prepare an electrode for an electrochemical storage device consisting of the following steps in the following order: (a) mixing solid xanthan gum with a source of conducting carbon particles and, optionally the active material by shear stress at about 400 rpm in intervals; (b) adding an active material to the resulting mixture obtained in step (a) in case the active material was not added or not sufficiently added in step (a); (c) drying the resulting mixture obtained in step (a) or (b); (d) adding water to the resulting mixture obtained in step (c) and stirring to form a flowable aqueous slurry composition such that the content of solids in the resulting aqueous slurry is between 2 and 25 wt. %; (e) spraying the flowable aqueous slurry composition consisting of water, xanthan gum, the conducting carbon particles and the active material on an electrode base to obtain a covered electrode base; and (f) drying the covered electrode base; wherein an improved adhesion is obtained between the electrode base and the coating formed by the sprayed flowable aqueous slurry composition.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 illustrates the charge and discharge specific capacities as a function of cycle number at a rate of C/5 for the sprayed LTO/Cu electrode prepared according to the invention (Example 1). The horizontal dotted line indicates the theoretical specific capacity of the active material.

(2) FIG. 2 illustrates the charge and discharge specific capacities as a function of cycle number at a rate of C/5 for the LTO/Cu electrodes processed by bar-coater of Example 3. The horizontal dotted line indicates the theoretical specific capacity of the active material.

(3) FIG. 3 illustrates the charge and discharge specific capacities as a function of cycle number and at different rates of C/5, C/2, 1C, 2C, 5C, 10C for the sprayed LTO/Cu electrode prepared according to the invention (example 1). The horizontal dotted line indicates the theoretical specific capacity of the active material.

(4) FIG. 4 illustrates the charge and discharge specific capacities as a function of cycle number and at different rates of C/5, C/2, 1C, 2C, 5C, 10C for the LTO/Cu electrodes processed by bar-coater of Example 3. The horizontal dotted line indicates the theoretical specific capacity of the active material.

(5) FIG. 5 illustrates the charge and discharge specific capacities as a function of cycle number and at different rates of C/5, C/2, 1C, 2C, 5C, 10C for the sprayed LFP/Al electrodes containing 75 wt. % LFP(LiFePO.sub.4) of example 6.

(6) FIG. 6 illustrates charge and discharge specific capacities as a function of cycle number and at different rates of C/5, C/2, 1C, 2C, 5C, 10C for the sprayed LFP/Al electrodes containing 70 wt. % LFP(LiFePO.sub.4) of example 6.

(7) FIG. 7 illustrates the charge and discharge specific capacities as a function of cycle number at a rate of C/5 for the sprayed Graphite/Cu electrode prepared according to the invention (as described in example 2). The dotted line indicates the theoretical specific capacity of the active material.

(8) FIG. 8 illustrates the charge and discharge specific capacities as a function of cycle number at different rates of C/5, C/2, 1C, 2C, 5C, 10C of the LTO (Li.sub.4Ti.sub.5O.sub.12, anode material) on a Cu disc electrode prepared according to the invention (as described in example 8) and the horizontal dotted line indicates the theoretical specific capacity of the active material.

(9) FIG. 9 illustrates the charge and discharge specific capacities as a function of cycle number at different rates of C/5, C/2, 1C, 2C, 5C, 10C of the LTO/Cu electrode as obtained by means of bar coater (procedure of Example 3) and the horizontal dotted line indicates the theoretical specific capacity of the active material.

(10) FIG. 10 illustrates the charge and discharge specific capacities as a function of cycle number at a rate of 1C in half-cells of sprayed LTO (Li.sub.4Ti.sub.5O.sub.12, anode material) on stainless steel current collectors prepared according to the invention (as described in example 9) and the horizontal dotted line indicates the theoretical specific capacity of the active material.

(11) FIG. 11 illustrates the charge and discharge specific capacities as a function of cycle number at C/5 and C/2, in half-cells of LCO (LiCoO.sub.2, cathode) for the electrode derived from the 75 wt. % LCO, 5 wt. % xanthan gum, 20 wt. % conducting carbon mixture and the horizontal dotted line indicates the theoretical specific capacity of the active material (as described in example 10).

(12) FIG. 12 illustrates at the charge and discharge specific capacities as a function of cycle number C/5 and C/2, in half-cells of LCO (LiCoO.sub.2, cathode) for the electrode derived from the 70 wt. % LCO, 5 wt. % xanthan gum, 25 wt. % conducting carbon mixture and the horizontal dotted line indicates the theoretical specific capacity of the active material (as described in example 10).

(13) FIG. 13 illustrates the gel-like mixture formed upon dissolving xanthan gum alone in water (FIGS. 13 A and B) and the gel-like mixture formed upon adding water to a hand-mixed solid mixture containing xanthan gum, conducting carbon and LiFePO.sub.4 (FIGS. 13 C and D). (as described in example 12).

(14) FIG. 14 consists of FIG. 14A and FIG. 14B, and illustrate the charge and discharge specific capacities as a function of cycle number, at a rate of C/5, for half-cells bearing either a LTO-anode (Li.sub.4Ti.sub.5O.sub.12) on a Cu disc or a LFP-cathode (LiFePO.sub.4) on an Al disk, prepared according to the invention and for comparison with data reported in US2013/0108776 (as described in example 13).

(15) FIG. 15 illustrates the charge and discharge specific capacities as a function of cycle number, at a rate of C/5, for half-cells bearing LFP-cathodes (LiFePO.sub.4) prepared as aqueous slurries and sprayed on Al disks. The slurries are prepared with different contents of Multiwalled Carbon Nanotubes NC7000 as conducting additive (0% in FIG. 15A; 2% in FIG. 15B; 15% in FIG. 15C; 50% in FIG. 15D; 100% in FIG. 15E) according to example 14.

(16) FIG. 16 illustrates the charge and discharge specific capacities as a function of cycle number, at a rate of C/5, for half-cells bearing LTO-anodes (Li.sub.4Ti.sub.5O.sub.12) prepared as aqueous slurries and sprayed on Cu disks. The slurries are prepared with different contents of Multiwalled Carbon Nanotubes NC7000 (0% in FIG. 16A; 2% in FIG. 16B; 15% in FIG. 16C; 50% in FIG. 16D; 100% in FIG. 16E) according to example 15.

(17) FIG. 17 illustrates adherence tests of LTO (Li.sub.4Ti.sub.5O.sub.12) based anodes on a Cu foil. Coatings were realized by bar-coating or manual spray, in aqueous as well as organic slurries, as described in example 16.

(18) FIG. 18 illustrates the charge and discharge specific capacities as a function of cycle number at a rate of C/10 for 20 cycles and C/2 for 80 cycles of a full Li-ion cell comprising an anode based on LTO (Li.sub.4Ti.sub.5O.sub.12) sprayed on a Cu disc and a cathode based on LFP (LiFePO.sub.4) sprayed on an Al disk, as described in example 17.

(19) FIG. 19 illustrates the charge and discharge specific capacities as a function of cycle number at a rate of C/10 for 20 cycles and C/2 for 80 cycles of a full Li-ion cell comprising an anode based on LTO (Li.sub.4Ti.sub.5O.sub.12) sprayed on a Cu disc and a cathode based on LFP (LiFePO.sub.4) sprayed on an Al disk, and wherein the conducting carbon additive of both the electrodes is composed of Multiwalled Carbon Nanotubes only, as described in example 18.

(20) FIG. 20 illustrates the charge and discharge specific capacities as a function of cycle number, at a rate of C/5, for a half-cell bearing an anode prepared with a commercial LTO (Li.sub.4Ti.sub.5O.sub.12) material and sprayed on a Cu disc, as described in example 19. The dotted line represents the theoretical capacity of the active material.

(21) FIG. 21 illustrates the charge and discharge specific capacities as a function of cycle number, at variable rates, for a half-cell bearing an anode prepared with a commercial LTO (Li.sub.4Ti.sub.5O.sub.12) material and sprayed on a Cu disc, as described in example 20. The dotted line represents the theoretical capacity of the active material.

DETAILED DESCRIPTION OF THE INVENTION

(22) The invention shall be illustrated by the following non-limiting examples.

Example 1

(23) This example describes the process of preparing various types of electrodes.

(24) 0.200 g xanthan gum (Binder, Sigma Aldrich) and 0.800 g Carbon Super C65 (Conducting Carbon, Timcal) were mixed in a planetary mill (Fritsch Monomill P6) in stainless-steel jars with 20 stainless-steel balls (diameter 10 mm). Mixing was performed at 400 rpm, 5×1 minute, 15 seconds pause and in reverse mode.

(25) Then, 0.125 g of this mixture were put together with 0.375 g of active material, either Li.sub.4Ti.sub.5O.sub.12 (anode material, as prepared for all examples unless stated otherwise by the procedure described in Kiyoshi Nakahara, et al., Preparation of particulate Li.sub.4Ti.sub.5O.sub.12 having excellent characteristics as an electrode active material for power storage cells, Journal of Power Sources 117 (2003) 131-136) or LiFePO.sub.4 (cathode material, Pholicat FE100 as obtained from beLife), leading to a composition by weight percentage of 75:20:5 (active material:conducting carbon:binder). This mixture was dried during 1 hour at 100° C. 3.6 g of MilliQ water were then added resulting in a slurry containing 12 wt. % solids, followed by magnetic stirring during 3 hours at 1000 rpm. The slurry was then sprayed on 20 pre-weighed current collector Cu disks in the case of anode materials (Ø 14 mm, punched from a copper foil, MTI corp.), on pre-weighed current collector Al disks in the case of cathode materials (Ø 14 mm, punched from an alimentary Reynolds Al foil)) and/or on pre-weighed current collector stainless-steel disks for both types of materials (Ø 15.5 mm, MTI corp.) using an airbrush (Harder & Steenbeck Airbrush Evolution Silverline fPc, 0.4 mm nozzle and needle). The coated disks were dried during 2 hours at ambient temperature and overnight at 60° C. The weight of active material was determined with very good accuracy (error lower than 1%) upon weighing the electrodes after drying and subtracting the mass of the corresponding bare current collector disk. An average mass of active material of 2.2 mg/cm.sup.2 was obtained regardless the used active material. The obtained electrodes were then dried at 120° C. under vacuum during 2 hours and transferred to an Ar-filled glove-box (MBraun) for making half-cell assemblies.

(26) The electrochemical measurements were carried out in CR2032 coin cells, where the tested material acted as cathode and a Li-metal disk as anode. A Celgard® separator soaked with 80 μL of LP71 (1 M LiPF6 in Ethylene carbonate:Diethylcarbonate:Dimethylcarbonate (EC:DEC:DMC) 1:1:1 weight ratios) or Ethylene carbonate Diethylcarbonate (EC:DEC) 1:1 weight ratio electrolyte was placed in-between. Charge-discharge cycles were recorded up to rates of 10C (6 minutes to fully charge the cell, 6 minutes to fully discharge the cell again) between 1.0 and 2.5 V (vs. Li.sup.+/Li) or 2.0 and 4.2 V (vs. Li.sup.+/Li) for anode and cathode materials respectively with a Biologic VMP3 multichannel potentiostat or a Neware battery cycler at 25° C.

Example 2

(27) Example 1 was repeated for preparing a graphite (anode material, KS6L, Timcal) covered electrode. In this example however no conducting carbon was added to the mixture. Briefly, 0.025 g of xanthan gum (Binder, Sigma Aldrich) was mixed with 0.475 g graphite (KS6L, Timcal), leading to a composition having a weight percentage of 95 wt. % graphite and 5 wt. % xanthan gum. This mixture was dried during 1 hour at 100° C. and 4.6 g of MilliQ water was subsequently added resulting in a slurry consisting of 9.8 wt. % solids. The next steps were as in Example 1. An average mass of active material of 3.6 mg/cm.sup.2 on the electrode was obtained.

Example 3 (Comparison)

(28) This example describes the preparation of LTO/Cu electrodes by means of a bar coater following a widely used conventional method. Li.sub.4Ti.sub.5O.sub.12 (LTO) (anode material, as prepared for all examples unless stated otherwise by the procedure described in Kiyoshi Nakahara, et al., Preparation of particulate Li.sub.4Ti.sub.5O.sub.12 having excellent characteristics as an electrode active material for power storage cells, Journal of Power Sources 117 (2003) 131-136) was dispersed in an organic solvent (NMP, N-methyl-2-pyrrolidone) with PVDF (polyvinylidene fluoride) as a binder. The chosen composition by mass was: 75 wt. % LTO, 10 wt. % PVDF, 15 wt. % Conducting Carbon (Super C65, Timcal). The obtained organic slurry was coated on a Cu-foil by bar-coater at ambient temperature. This foil was then dried at 60° C. and 14-mm electrodes were punched from this coating. The mass of active material was determined upon weighing these electrodes and subtracting the average mass of bare Cu-disks of the same size.

Example 4

(29) In this example the cycling performance at C/5 in half-cells of LTO (Li.sub.4Ti.sub.5O.sub.12, anode material) on a Cu disc according to the invention and as obtained in Example 1 were compared to the cycling performance at C/5 for the LTO/Cu disc as obtained by means of bar coater in Example 3.

(30) Galvanostatic cycling was performed at a rate of C/5 (5 hours needed to fully charge the cell, 5 hours to fully discharge the cell).

(31) FIG. 1 shows the charge and discharge specific capacities as a function of cycle number and the horizontal dotted line indicates the theoretical specific capacity of the active material for the sprayed LTO/Cu electrode of Example 1. The specific capacity after 20 cycles was 163 mAh/g.

(32) FIG. 2 shows the charge and discharge specific capacities as a function of cycle number and the horizontal dotted line indicates the theoretical specific capacity of the active material for the bar coater LTO/Cu electrode of Example 3. The specific capacity after 20 cycles was 166 mAh/g.

(33) This experiment shows that the specific capacity after 20 cycles of the sprayed LTO/Cu electrode of Example 1 is very close to that of the bar coater LTO/Cu electrode of Example 3, and the cycling stability is the same. The observed differences cannot be considered as significant owing to the errors occurring on the mass determinations of electrodes obtained by the organic bar-coating process.

Example 5

(34) In this example the cycling performance at variable rates in half-cells of LTO (Li.sub.4Ti.sub.5O.sub.12, anode material) on a Cu disc according to the invention and as obtained in Example 1 were compared to the cycling performance at variable rates for the LTO/Cu disc as obtained by means of bar coater in Example 3.

(35) Galvanostatic cycling was performed first at a rate of C/5 (5 hours needed to fully charge the cell, 5 hours to fully discharge the cell) for a given number of cycles, followed by cycling at higher rates (C/2, 1C, 2C, 5C, 10C and back to C/5), for 10 cycles at each rate. (10C: 6 minutes needed to fully charge the cell, 6 minutes to fully discharge the cell).

(36) FIG. 3 shows the charge and discharge specific capacities as a function of cycle number and the horizontal dotted line indicates the theoretical specific capacity of the active material for the sprayed LTO/Cu electrode of Example 1. FIG. 4 shows the charge and discharge specific capacities as a function of cycle number and the horizontal dotted line indicates the specific theoretical capacity of the active material for the bar coater LTO/Cu electrode of Example 3.

(37) The specific capacity per cycle is also listed in the below Table 1.

(38) TABLE-US-00001 TABLE 1 Specific capacity Specific capacity Rate Example 1 (mAh/g) Example 3 (mAh/g) C/5 162 166 C/2 159 163 C 143 160  2C 133 143  5C 66 104 10C 30 70 C/5 162 165

(39) The global behavior is the same for the electrodes of Example 1 (aqueous slurry) and Example 3 (organic slurry). The comparison of specific capacities reported in the Table 1 shows that the performances are somewhat lower in the case of the aqueous coatings, especially at high rates (5C and 10C). Full recovery of specific capacity at C/5 after cycling at high rates is observed in both cases.

Example 6

(40) Example 6 shows the cycling performance in half-cells of LFP (LiFePO.sub.4, cathode material, Pholicat FE100, beLife) at variable rates for aqueous sprayed slurries, with different contents in active material.

(41) Two electrodes were prepared according to the procedure of Example 1: 75 wt. % LFP, 5 wt. % xanthan gum, 20 wt. % Conducting Carbon (Super C65, Timcal) and 70 wt. % LFP, 5 wt. % xanthan gum, 25 wt. % Conducting Carbon (Super C65, Timcal). The fraction of total solids in water was 12 wt. %. The obtained aqueous slurry was then sprayed at ambient temperature on pre-weighed 14-mm Al-disks. The electrodes were weighed after drying at 60° C., allowing for the precise determination of the mass of active material.

(42) Galvanostatic cycling was performed first at a rate of C/5 (5 hours needed to fully charge the cell, 5 hours to fully discharge the cell) for a given number of cycles, followed by cycling at higher rates (C/2, 1C, 2C, 5C, 10C), with 10 cycles of charge-discharge at each rate. This procedure was repeated 3 times on the same cell.

(43) FIG. 5 shows the charge and discharge specific capacities as a function of cycle number for the electrode with 75 wt. % LFP and FIG. 6 shows the charge and discharge specific capacities as a function of cycle number for the electrode with 70 wt. % LFP.

(44) For both contents of LFP, stable cycling is observed up to 2C (30 minutes needed to fully discharge the cell, 30 minutes to fully charge again), with high values of specific capacities. Superior performances in terms of capacity at high rates are obtained when the content of LFP decreases from 75 to 70 wt. %, i.e. when the relative quantity of conducting carbon is increased.

(45) In each case, the specific capacities are recovered after cycling at very high rates, indicating the stability of the coatings.

Example 7

(46) Example 7 shows the cycling performance in a half-cell of Graphite (KS6L, anode material, Timcal) at C/5 for an aqueous sprayed slurry. The electrode was prepared as described in Example 2 on 14-mm Cu-disks. The horizontal dotted line indicates the theoretical specific capacity of the active material for the sprayed Graphite/Cu electrode of Example 2.

(47) Galvanostatic cycling was performed at a rate of C/5 (5 hours needed to fully charge the cell, 5 hours to fully discharge the cell).

(48) FIG. 7 and the Table 2 below show the charge and discharge specific capacities as a function of cycle number and the dotted line indicates the theoretical specific capacity of the active material.

(49) TABLE-US-00002 TABLE 2 Specific capacity Cycle (mAh/g) 1 320 10 339 25 340 50 336 75 324 100 317

(50) A specific capacity of about 340 mAh/g, which remains stable for 50 cycles, is obtained for this coating, which corresponds to 91% of the theoretical specific capacity of graphite. A slow decay is then observed, which could be attributed to the fact that no conducting carbon was added to the solid mixture.

Example 8

(51) In this example the cycling performance at variable rates in half-cells of LTO (Li.sub.4Ti.sub.5O.sub.12, anode material) on a Cu disc according to the invention were compared to the cycling performance at variable rates for the LTO/Cu disc as obtained by means of bar coater in Example 3.

(52) The LTO (Li.sub.4Ti.sub.5O.sub.12, anode material) on a Cu disc electrode was prepared according to Example 1, except in that the active material is directly mixed with the conductive carbon and the binder in weight percentages of 80:15:5 or 75:20:5 (active material:conducting carbon:xanthan gum). This mixture is dried during 1 hour at 100° C. and then subjected to planetary milling following the same procedure as described for Example 1, allowing for a more intimate contact between the components of the solid mixture. The latter is then dispersed in MilliQ water (12 wt. % solids), followed by magnetic stirring and spraying at ambient temperature on pre-weighed 14-mm Cu-disks. The electrodes were weighed after drying at 60° C., allowing for the precise determination of the mass of active material.

(53) Galvanostatic cycling was performed first at a rate of C/5 (5 hours needed to fully charge the cell, 5 hours to fully discharge the cell) for a given number of cycles, followed by cycling at higher rates (C/2, 1C, 2C, 5C, 10C and back to C/5), for 10 cycles at each rate. (10C: 6 minutes needed to fully charge the cell, 6 minutes to fully discharge the cell)

(54) FIG. 8 shows the charge and discharge specific capacities as a function of cycle number of the LTO (Li.sub.4Ti.sub.5O.sub.12, anode material) on a Cu disc electrode prepared according to the procedure of the above paragraph and the horizontal dotted line indicates the theoretical specific capacity of the active material. FIG. 9 shows the charge and discharge specific capacities as a function of cycle number of the LTO/Cu electrode as obtained by means of bar coater (procedure of Example 3) and the horizontal dotted line indicates the theoretical specific capacity of the active material.

(55) The global behavior is the same for the aqueous and organic slurries. Improved specific capacities for each rate of cycling are however obtained in the case of the aqueous pathway with xanthan gum as a binder.

(56) The comparison of these results with Example 5 suggests that the optional addition of the active material (step aii) to the xanthan gum—conducting carbon mixture prior to ball-milling is more adapted for insulating active materials. Indeed, the ball-milling step of all the components will lead to an enhanced interaction between the LTO active material and the conducting carbon additive, which will result in enhanced cycling performances, especially at high rates, favoring the electron transfers.

Example 9

(57) Example 9 illustrates the cycling performance in half-cells of LTO (Li.sub.4Ti.sub.5O.sub.12, anode material) at 1C for aqueous sprayed slurries with stainless-steel disks as current collectors.

(58) The LTO (Li.sub.4Ti.sub.5O.sub.12, anode material) on a stainless-steel (SS) disc electrode was prepared according to Example 1, except in that the active material is directly mixed with the conductive carbon and the binder in weight percentages of 80:15:5 or 75:20:5 (active material:conducting carbon:xanthan gum). This mixture is dried during 1 hour at 100° C. and then subjected to planetary milling following the same procedure as described for Example 1, allowing for a more intimate contact between the components of the solid mixture. The latter is then dispersed in MilliQ water (12 wt. % solids), followed by magnetic stirring and spraying at ambient temperature on pre-weighed 15.5-mm SS-disks. The electrodes were weighed after drying at 60° C., allowing for the precise determination of the mass of active material.

(59) Galvanostatic cycling was performed at a rate of 1C (1 hour needed to fully charge the cell, 1 hour to fully discharge the cell).

(60) FIG. 10 shows the charge and discharge specific capacities as a function of cycle number and the horizontal dotted line indicates the theoretical specific capacity of the active material. An excellent cycling stability with a stable value of specific capacity of 161 mAh/g up to 150 cycles at least was recorded in this case.

Example 10

(61) Example 10 shows the cycling performance in half-cells of LCO (LiCoO.sub.2, cathode material, Sigma-Aldrich) at C/5 and C/2 for aqueous sprayed slurries, with different contents in active material.

(62) For the dispersion in water, the procedure of Example 1 was first used. No cycling of half-cells could be performed in this case, probably due to improper contact between the active material and the conducting carbon additive.

(63) For that reason the active material is directly mixed with the conductive carbon and the binder in weight percentages of 75 wt. % LCO, 5 wt. % xanthan gum, 20 wt. % conducting carbon (Super C65, Timcal) and 70 wt. % LCO, 5 wt. % xanthan gum, 25 wt. % conducting carbon (Super C65, Timcal). This mixture is dried during 1 hour at 100° C. and then subjected to planetary milling following the same procedure as described for Example 1, allowing for a more intimate contact between the components of the solid mixture. The latter is then dispersed in MilliQ water (12 wt. % solids), followed by magnetic stirring and spraying at ambient temperature on pre-weighed 14-mm Al-disks. The electrodes were weighed after drying at 60° C., allowing for the precise determination of the mass of active material.

(64) Galvanostatic cycling was performed first for 100 cycles at a rate of C/5 (5 hours needed to fully charge the cell, 5 hours to fully discharge the cell), followed by cycling at C/2 (2 hours needed to fully charge the cell, 2 hours to fully discharge the cell).

(65) FIG. 11 shows the charge and discharge specific capacities as a function of cycle number for the electrode derived from the 75 wt. % LCO, 5 wt. % xanthan gum, 20 wt. % conducting carbon mixture. FIG. 12 shows the charge and discharge specific capacities as a function of cycle number for the electrode derived from the 70 wt. % LCO, 5 wt. % xanthan gum, 25 wt. % conducting carbon mixture.

(66) For both contents of LCO, the specific capacity tends to decrease with cycling. A better stability and higher specific capacity values are observed when the relative amount of conducting carbon is increased (70 wt. % of LCO), demonstrating the importance of the contact between the additive and the active material.

(67) Although the cycling stability is not optimized, this example nevertheless demonstrated the possibility of coating another cathode material than LFP by aqueous processing, with xanthan gum as a binder. Improved performances are expected upon using modified or pre-treated LCO.

(68) This example also demonstrates the benefits of the modified procedure when the active materials used display an insulating character.

Example 11

(69) Li.sub.4Ti.sub.5O.sub.12 coated on Cu and SS electrodes as well as LiFePO.sub.4 coated on Al and SS electrodes, prepared as described in the above Examples 4, 5, 6, by the aqueous pathway according to the processes of this invention, were recovered after cell disassembly. The electrodes were covered with 3.5 ml of deionized water without any prior treatment. After contacting by manual stirring or ultrasounds for 10 seconds at ambient temperature, the coatings separated from the current collectors, allowing for the recovery of clean metal bases (Cu, Al or SS). This example demonstrates the benefits of the invention by the fact that a non-toxic solvent (water) can easily be used to recover clean metal current collectors after batteries end-of-life.

Example 12

(70) Example 12 shows a preferred embodiment wherein a shear stress is applied to the solid components prior to the slurry preparation to obtain a flowable sprayable solution

(71) In a first instance, 0.025 g of Xanthan gum binder, i.e. the quantity corresponding to that described in Example 1, was dissolved in 3.6 g of MilliQ water, followed by magnetic stirring during 3 hours at 1000 rpm. A gel-like mixture is formed as illustrated in FIGS. 13 A and B, which cannot be processed further, e.g. by spraying.

(72) On the opposite, if the xanthan gum binder is ball-milled with a carbon additive, as reported in Example 1, the resulting solid mixture can be dispersed in water in presence of a cathode or anode active material, leading to a low viscosity sprayable solution.

(73) In a second instance, 0.025 g xanthan gum binder, 0.100 g of Carbon Super C65 (Conducting Carbon, Timcal) and 0.375 g of LiFePO.sub.4 (cathode material, Pholicat FE100 as obtained from beLife), were hand-mixed in a vial, leading to a composition by weight percentage of 75:20:5 (active material:conducting carbon:binder). To this mixture, 3.6 g of MilliQ water were then added, resulting in a slurry containing 12 wt. % solids, followed by magnetic stirring during 3 hours at 1000 rpm. A gel-like mixture is formed as illustrated in FIG. 13 C&D, which cannot be further processed either by spraying or by bar-coater in opposition to the process according to the invention, wherein a flowable sprayable solution is obtained.

Example 13 Comparison with US US2013/0108776A1

(74) This example shows the cycling performance at C/5 in half-cells of LTO (Li.sub.4Ti.sub.5O.sub.12, anode material) on a Cu disc and LFP (LiFePO.sub.4, cathode material, Pholicat FE100, beLife) on an Al disk, according to the invention and as obtained in Example 1. Charge and discharge were performed at this rate during 50 cycles to evaluate the stability over time.

(75) As shown from FIG. 14 and Table 3, the specific capacities remain stable for both of the investigated active materials when cycling is performed during 50 cycles at a rate of C/5. This is opposite to the observations described in US2013/0108776A1, wherein polyethyleneimine is needed as a dispersant for slurry preparation. In this latter case, the specific capacity of LiFePO.sub.4 cathode materials decreases with cycling when no polyethyleneimine is added to the mixture. This difference proves that the process according to the invention can lead to electrodes (anodes and cathodes) with a good cycling stability, without need of an additional dispersant in the mixture.

(76) TABLE-US-00003 TABLE 3 Specific capacity Specific capacity Cycle (mAh/g) - LTO anode (mAh/g) - LFP cathode 1 153 145 10 153 143 25 152 146 50 152 147

Example 14

(77) Example 14 shows the cycling performance in half-cells of LFP (LiFePO.sub.4, cathode material, Pholicat FE100, beLife) at a rate of C/5 for aqueous sprayed slurries on Al disks, with different contents of Multiwalled Carbon Nanotubes (MWCNT, NC-7000, Nanocyl) as a conducting additive.

(78) The electrodes were prepared according to the procedure of Example 1: 75 wt. % LFP, 5 wt. % xanthan gum, 20 wt. % Conducting additive. The classically used Conducting Carbon additive (Super C65, Timcal) was in this case replaced by 2, 15, 50 and 100 wt. % carbon nanotubes. The fraction of total solids in water was 12 wt. %. The obtained aqueous slurry was then sprayed at ambient temperature on pre-weighed 14-mm Al-disks. The electrodes were weighed after drying at 60° C., allowing for the precise determination of the mass of active material.

(79) Galvanostatic cycling was performed during 50 cycles at C/5 (5 hours needed to fully charge the cell, 5 hours to fully discharge the cell).

(80) FIG. 15 represents the charge and discharge specific capacities as a function of cycle number and Table 4 shows the discharge capacity at cycle 50 for each composition.

(81) TABLE-US-00004 TABLE 4 Specific discharge CNT contents capacity @ cycle 50 (wt. %) (mAh/g) 0 147 2 146 15 148 50 150 100 147

(82) Stable cycling is observed at C/5 whatever the contents in carbon nanotubes as a conducting carbon additive. Indeed, even with full replacement of the classically used Super C65, i.e. 100% CNT, similar values of capacities are obtained for this cycling. The values of specific discharge capacity also remain in the same range after 50 cycles, with values comprised between 146 and 150 mAh/g. These results prove that the procedure presented here is compatible with the dispersion of multiwalled carbon nanotubes in aqueous slurries for Li-ion battery electrodes preparation.

Example 15

(83) Example 15 shows the cycling performance in half-cells of LTO (Li.sub.4Ti.sub.5O.sub.12, anode material) at a rate of C/5 for aqueous sprayed slurries on Cu discs, with different contents of Multiwalled Carbon Nanotubes (MWCNT, NC-7000, Nanocyl) as a conducting additive.

(84) The electrodes were prepared according to the procedure of Example 1: 75 wt. % LTO, 5 wt. % xanthan gum, 20 wt. % Conducting additive. The classically used Conducting Carbon additive (Super C65, Timcal) was in this case replaced by 2, 15, 50 and 100 wt. % carbon nanotubes. The fraction of total solids in water was 12 wt. %. The obtained aqueous slurry was then sprayed at ambient temperature on pre-weighed 14-mm Cu-disks. The electrodes were weighed after drying at 60° C., allowing for the precise determination of the mass of active material.

(85) Galvanostatic cycling was performed during 50 cycles at C/5 (5 hours needed to fully charge the cell, 5 hours to fully discharge the cell).

(86) FIG. 16 represents the charge and discharge specific capacities as a function of cycle number and Table 5 shows the discharge capacity at cycle 50 for each composition.

(87) TABLE-US-00005 TABLE 5 Specific discharge CNT contents capacity @ cycle 50 (wt. %) (mAh/g) 0 152 2 159 15 147 50 147 100 156

(88) Stable cycling is observed at C/5 whatever the contents in carbon nanotubes as a conducting carbon additive. Indeed, even with full replacement of the classically used Super C65, i.e. 100% CNT, similar values of capacities are obtained for this cycling. The values of specific discharge capacity also remain in the same range after 50 cycles, with values comprised between 147 and 159 mAh/g. These results prove that the procedure presented here is compatible with the dispersion of multiwalled carbon nanotubes in aqueous slurries for Li-ion battery electrodes preparation.

Example 16

(89) This example illustrates the improved behavior in terms of adhesion of the coatings obtained by the process according to the invention. Three coatings have been prepared for an anode active material (LTO, Li.sub.4Ti.sub.5O.sub.12, anode material on a Cu foil according to the invention and as obtained in Example 1. Two different coating techniques have been used, namely bar-coater and manual spray. The classical composition made of PVDF binder in NMP solvent has also been compared with the aqueous pathway using XG as a binder. No further treatment was applied to the substrates prior to the coatings. This is opposite to US2013/0108776A1, where a surface treatment, e.g. plasma corona treatment is applied in order to raise the surface energy of the surface to at least the surface tension of the mixed dispersion.

(90) The adhesion has been tested for three types of coatings in each case by the use of the ASTM D3359-97 procedure. This test is based on the application of a force or an energy to separate two materials linked by a common surface. Adhesive paper is used to peel off the coating with an angle of 180°.

(91) In the present case, the adhesion was qualitatively evaluated upon observation of the substrate as well as of the adhesive paper after the test.

(92) FIG. 17 shows adhesion results in different conditions for LTO active material on a copper foil. On the left side is shown a picture of the copper foil after the adhesion test and on the right side a picture of the corresponding adhesive paper after the test.

(93) The results clearly show that the process according to the invention using water and manual spray as coating method displays the better behavior in terms of adhesion when compared with another coating technique (bar-coater) or with another ink preparation process (NMP+PVDF). Indeed, more coating remains present on the copper foil when the process according to the invention is used, and less material is seen on the adhesive paper in this case. This experiment demonstrates that the spraying technique leads to distinguished features in comparison to the bar-coating process, in addition to the fact that the water-based slurry making use of xanthan gum also shows superiority in terms of adhesion in comparison to the organic pathway.

Example 17

(94) Example 17 shows the cycling performance at C/10 for 20 cycles and at C/2 for 80 cycles of a full Li-ion cell comprising an anode based on LTO (Li.sub.4Ti.sub.5O.sub.12, anode material) on a Cu disc and a cathode based on LFP (LiFePO.sub.4, cathode material, Pholicat FE100, beLife) on an Al disk, according to the invention and as obtained in Example 1. Both electrodes were assembled in a CR2032 coin cell, with a Celgard® separator soaked with 80 μL of LP71 (1 M LiPF.sub.6 in Ethylene carbonate:Diethylcarbonate Dimethylcarbonate (EC:DEC:DMC) 1:1:1 weight ratios) electrolyte was placed in-between. The charge-discharge cycles were recorded between 1.0 and 2.5 V (vs. Li.sup.+/Li) with a Biologic VMP3 multichannel potentiostat or a Neware battery cycler at 25° C.

(95) As shown from FIG. 18 and Table 6, a good cycling stability is recorded either at a rate of C/10 (10 hours to fully charge the cell, 10 hours to fully discharge it) as well as at C/2. The specific capacity of the cell is given as a function of the mass of LFP-cathode material. In this latter case, the specific capacity of the full cell stabilizes at ˜115 mAh/g .sub.LFP, i.e. 115 mAh per gram of LFP present at the cathode.

(96) These results indicate that the process described in the invention can lead to electrodes (anodes and cathodes) that work well in a Li-ion full cell, with good cycling stability.

(97) TABLE-US-00006 TABLE 6 Specific capacity Cycle Rate (mAh/g.sub.LFP) 5 C/10 138 15 137 25 C/2  125 50 120 100 116

Example 18

(98) This Example shows the cycling performance at C/10 for 20 cycles and at C/2 for 80 cycles of a full Li-ion cell comprising an anode based on LTO (Li.sub.4Ti.sub.5O.sub.12, anode material) on a Cu disc and a cathode based on LFP (LiFePO.sub.4, cathode material, Pholicat FE100, beLife) on an Al disk, according to the invention and as obtained in Examples 14 and 15. In this case, for both the electrodes, the conducting carbon additive was totally replaced with multiwalled carbon nanotubes (Nanocyl NC-7000). Both electrodes were assembled in a CR2032 coin cell, with a Celgard® separator soaked with 80 μL of LP71 (1 M LiPF.sub.6 in Ethylene carbonate:Diethylcarbonate:Dimethylcarbonate (EC:DEC:DMC) 1:1:1 weight ratios) electrolyte was placed in-between. The charge-discharge cycles were recorded between 1.0 and 2.5 V (vs. Li.sup.+/Li) with a Biologic VMP3 multichannel potentiostat or a Neware battery cycler at 25° C.

(99) As shown from FIG. 19 and Table 7, a good cycling stability is recorded either at a rate of C/10 (10 hours to fully charge the cell, 10 hours to fully discharge it) as well as at C/2. The specific capacity of the cell is given as a function of the mass of LFP-cathode material. In this latter case, the specific capacity of the full cell stabilizes at ˜105 mAh/g .sub.LFP, i.e. 115 mAh per gram of LFP present at the cathode

(100) These results indicate that the process described in the invention can lead to electrodes (anodes and cathodes) bearing only multiwalled carbon nanotubes as a conducting additive that work well in a Li-ion full cell, with good cycling stability. The performances remain comparable to those recorded for a full cell assembled from electrodes prepared according to the invention and as described in Example 1, with Timcal Super C65 as a conducting additive.

(101) TABLE-US-00007 TABLE 7 Specific capacity Cycle Rate (mAh/g.sub.LFP) 5 C/10 129 15 130 25 C/2  115 50 109 100 106

Example 19

(102) In Example 19 the cycling performance at C/5 in half-cells of LTO (as-prepared particulate Li.sub.4Ti.sub.5O.sub.12, anode material) on a Cu disc according to the invention and as obtained in Example 1 were compared to the cycling performance at C/5 for a commercial LTO (Sigma-Aldrich, Lithium Titanate, Spinel, >99%) on a Cu disc, processed in the same way as described in Example 1.

(103) Galvanostatic cycling was performed at a rate of C/5 (5 hours needed to fully charge the cell, 5 hours to fully discharge the cell).

(104) FIG. 20 shows the charge and discharge specific capacities as a function of cycle number and the horizontal dotted line indicates the theoretical specific capacity of the active material for the sprayed commercial LTO/Cu electrode, which can be compared with the sprayed LTO/Cu electrode as obtained from Example 1 and illustrated in FIG. 1.

(105) The specific capacity in the present case after 20 cycles was 164 mAh/g, the same value as for the as-prepared particulate LTO/Cu electrode obtained from example 1 (163 mAh/g).

(106) The specific capacity per cycle is also listed in the below Table 8.

(107) TABLE-US-00008 TABLE 8 Specific capacity Specific capacity Cycle Example 1 (mAh/g) Example 19 (mAh/g) 1 163 166 10 163 164 20 163 164 50 — 162

(108) The global behavior is the same for the electrodes of Example 1 (as-prepared particulate LTO) and Example 19 (commercial LTO). The comparison of specific capacities reported in the Table 8 shows that the performances are identical, whatever the origin of the used anode active material.

Example 20

(109) In this example the cycling performance at variable rates in half-cells of LTO (as-prepared particulate Li.sub.4Ti.sub.5O.sub.12, anode material) on a Cu disc according to the invention and as obtained in Example 1 were compared to the cycling performance at variable rates for a commercial LTO (Sigma-Aldrich, Lithium Titanate, Spinel, >99%) on a Cu disc, processed in the same way as described in Example 1.

(110) Galvanostatic cycling was performed in both cases first at a rate of C/5 (5 hours needed to fully charge the cell, 5 hours to fully discharge the cell) for a given number of cycles, followed by cycling at higher rates (C/2, 1C, 2C, 5C, 10C and back to C/5), for 10 cycles at each rate. (10C: 6 minutes needed to fully charge the cell, 6 minutes to fully discharge the cell).

(111) FIG. 21 shows the charge and discharge specific capacities as a function of cycle number and the horizontal dotted line indicates the theoretical specific capacity of the active material for the sprayed commercial LTO/Cu electrode, which can be compared with the sprayed LTO/Cu electrode as obtained from Example 1 and illustrated in FIG. 3.

(112) The specific capacity per cycle is also listed in the below Table 9.

(113) TABLE-US-00009 TABLE 9 Specific capacity Specific capacity Rate Example 1 (mAh/g) Example 20 (mAh/g) C/5 162 162 C/2 159 152 C 143 143  2C 133 121  5C 66 78 10C 30 27 C/5 162 161

(114) The global behavior is the same for the electrodes of Example 1 (as-prepared particulate LTO) and Example 20 (commercial LTO). The comparison of specific capacities reported in the Table 9 shows that the performances are in the same range, whatever the origin of the used anode active material. Full recovery of specific capacity at C/5 after cycling at high rates is also observed in both cases.