Carbon-coated active particles and processes for their preparation

Abstract

This application describes a process for the preparation of carbon-coated particles, where the particles comprise an electrochemically active material. The process comprises the steps of emulsion polymerization, drying and thermally treating the polymer to obtain a nano-layer of carbon on the particles, where the carbon layer comprises fibers and nitrogen-containing polyaromatics have a graphene-like structure. The application also further relates to the particles produced by the method as well as to electrode materials, electrodes and electrochemical cells comprising the particles.

Claims

1. Carbon-coated particles, comprising: particles comprising a porous electrochemically active material; and a nano-layer of electron conductive carbon coating disposed on the surface and within a plurality of pores of said particles, the nano-layer of electron conductive carbon coating comprising carbon fibers and polyaromatics consisting of carbon and nitrogen atoms , wherein the nano-layer of electron conductive carbon coating consists of about 4 wt % to about 15 wt % of nitrogen atoms, the rest being carbon atoms.

2. The carbon-coated particles according to claim 1, wherein the nano-layer of electron conductive carbon coating has an average thickness of below 20 nm.

3. The carbon-coated particles according to claim 1, wherein the carbon-coated particles have a surface area of between about 2 m.sup.2/g and about 20 m.sup.2/g.

4. The carbon-coated particles of claim 3, wherein the surface area is of about 8 m.sup.2/g.

5. The carbon-coated particles of claim 1, wherein the electrochemically active material comprises a material selected from the group consisting of titanates, lithium titanates, lithium metal phosphates, vanadium oxides, lithium metal oxides, silicon, silicon oxides and combinations thereof.

6. The carbon-coated particles of claim 5, wherein the electrochemically active material is selected from TiO.sub.2, Li.sub.2TiO.sub.3, Li.sub.4Ti.sub.5O.sub.12, H.sub.2Ti.sub.5O.sub.11 and H.sub.2Ti.sub.4O.sub.9, or a combination thereof, LiM′PO.sub.4 wherein M′ is Fe, Ni, Mn, Co, or a combination thereof, LiV.sub.3O.sub.8, V.sub.2O.sub.5, LiMn.sub.2O.sub.4, LiM″O.sub.2, wherein M″ is Mn, Co, Ni, or a combination thereof, Li(NiM′″)O.sub.2, wherein M′″ is Mn, Co, Al, Fe, Cr, Ti, or Zr, and combinations thereof.

7. An electrode material comprising the carbon-coated particles of claim 1 together with a binder.

8. The electrode material of claim 7, wherein the binder is selected from SBR (styrene butadiene rubber), PAA (poly(acrylic acid)), PMAA (poly(methacrylic acid)), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), NBR (butadiene acrylonitrile rubber), HNBR (hydrogenated NBR), CHR (epichlorohydrin rubber), ACM (acrylate rubber), and combination thereof, optionally comprising a thickening agent such as carbomethoxy cellulose (CMC).

9. The electrode material of claim 8, wherein the binder comprises PAA or PMAA in combination with a binder selected from SBR, NBR, HNBR, CHR, ACM, and combinations thereof.

10. An electrode comprising the electrode material as defined in claim 7 on a current collector.

11. An electrochemical cell comprising an electrode as defined in claim 10, an electrolyte and a counter-electrode.

12. The carbon-coated particles according to claim 2, wherein the nano-layer of electron conductive carbon coating has an average thickness of below 10 nm.

13. The carbon-coated particles according to claim 2, wherein the nano-layer of electron conductive carbon coating has an average thickness of below 5 nm.

14. The carbon-coated particles according to claim 2, wherein the nano-layer of electron conductive carbon coating has an average thickness of below 2 nm.

15. The carbon-coated particles according to claim 1, wherein the nano-layer of electron conductive carbon coating consists of about 6 wt % to about 11 wt % of nitrogen atoms, the rest being carbon atoms.

16. The carbon-coated particles according to claim 3, wherein the carbon-coated particles have a surface area of between about 4 m.sup.2/g and about 15 m.sup.2/g.

17. The carbon-coated particles according to claim 3, wherein the carbon-coated particles have a surface area of between about 6 m.sup.2/g and about 10 m.sup.2/g.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a schematic illustration of an emulsion polymerization reaction, showing the diffusion of the monomer according to one embodiment.

(2) FIG. 2 shows four Scanning Electron Microscope (SEM) images of carbon-coated active particles according to one embodiment and comprising 1.5 wt % (a and b), and 1.0 wt % (c and d) of activated carbon.

(3) FIG. 3 shows two Transmission Electron Microscopy (TEM) images of a carbon-coated active particle according to one embodiment and comprising 1.5 wt % of activated carbon.

(4) FIG. 4 shows four TEM images of a carbon-coated active particle (1.0 wt. % activated carbon) according to one embodiment: a cross section of a carbon coating LTO particle (A); a layer of carbon inside a large pore (B); small pores filled with activated carbon (C); a zoom on a small pore (D).

(5) FIG. 5 shows the charge and discharge curves after the first and second cycles for a lithium half cell comprising (a) a LTO reference electrode; and (b) a LTO electrode comprising carbon-coated active particles (1.0 wt. % C) according to one embodiment.

(6) FIG. 6 shows the charge and discharge curves after the first and second cycles for a LFP-LTO full cell comprising (a) a LTO reference electrode; and (b) a LTO electrode comprising carbon-coated active particles (1.0 wt % C) according to one embodiment.

(7) FIG. 7 shows Nyquist plots of a LTO electrode comprising carbon-coated active particles according to one embodiment (where the carbon content is 1.0 wt %), and a reference electrode comprised in (a) a LFP-LTO full cell, and (b) a LTO lithium half cell.

(8) FIG. 8 shows the (a) charge and (b) discharge capacity retention at 1C, 2C, 4C and 10C for: a reference electrode; a commercial carbon-coated LTO electrode; and a C-LTO electrode comprising carbon-coated active particles (1.0 wt % C) according to one embodiment.

(9) FIG. 9 shows charge and discharge Direct Current Internal Resistance (DCIR) for: a reference electrode; a commercial carbon-coated LTO electrode; and a C-LTO electrode comprising carbon-coated active particles (1.0 wt % C) according to one embodiment.

DETAILED DESCRIPTION

(10) This application relates to a process for the preparation of electrode active material, more specifically, carbon-coated electrochemically active inorganic particles.

(11) In the present technology, the carbon coating is achieved by emulsion polymerization. This process is green and allows for the direct use of water dispersion in spray drying without further purification. For instance, the method comprises the following three main steps: 1) emulsion polymerization of poly(acrylonitrile) on inorganic particles, 2) evaporation of volatile components by spray-drying resulting in dried polymer-coated particles, and 3) carbonization of the polymer to form a carbon coating comprising carbon fibers. For instance, the carbonization step is achieved by heat treatment as described in Rahaman, M. S. A. et al., Polymer Degradation and Stability, 2007, 92 (8), 1421-1432.

(12) The particles to be coated using the present method include inorganic particles of electrochemically active materials, such as metal oxides and complex oxides. Examples of electrochemically active materials include, without limitation, titanates and lithium titanates (e.g.

(13) TiO.sub.2, Li.sub.2TiO.sub.3, Li.sub.4Ti.sub.5O.sub.12, H.sub.2Ti.sub.5O.sub.11, H.sub.2Ti.sub.4O.sub.9), phosphates (e.g. LiM′PO.sub.4 where M′ is Fe, Ni, Mn, Co, or a combination thereof), vanadium oxides (e.g. LiV.sub.3O.sub.8, V.sub.2O.sub.5, and the like), and other lithium and metal oxides such as LiMn.sub.2O.sub.4, LiM″O.sub.2 (M″ being Mn, Co, Ni, or a combination thereof), Li(NiM′″)O.sub.2 (M′″ being Mn, Co, Al, Fe, Cr, Ti, Zr, and the like, or a combination thereof), or a combination thereof. The particles are freshly formed or obtained from a commercial source and may be microparticles or nanoparticles.

(14) A first step in the present process is the use of emulsion polymerization. In the present method, inorganic particles serve as surfactant for the stabilisation of the emulsion. This method is generally known in the field as a “Pickering Emulsion”. At this stage, droplets of monomers (e.g. acrylonitrile) and radical initiator form at the surface and inside the pores of the inorganic particles dispersed in a solvent, e.g. water and/or an alcohol, preferably water or a combination of water and an alcohol. The emulsion can be obtained, for instance, by sonication, high power stirring or any other methods for forming droplets on particles' surface. Polymerization is then initiated and results in the polymer forming on the surface of the primary particles to produce a nano-layer of polymer (e.g. poly(acrylonitrile), also called PAN) (see FIG. 1).

(15) The dispersion obtained from the previous step after polymerization is then used directly for drying (e.g. spray-drying), i.e. without further purification. The temperature used in the drying step is above the boiling point of the solvent and the volatile material to be removed. For example, the temperature of the spray-dryer chamber is above 100° C., or between 100° C. and 120° C., or the temperature of the spray-dryer head is adjusted to between 120° C. and 250° C., or between 150° C. and 200° C. This process allows for the evaporation of the solvent and the residual volatile monomers. This step results in the particles being coated by a nano-layer of poly(acrylonitrile) polymer.

(16) After drying, the obtained coated particles are subjected to polymer degradation, for instance, by thermal treatment (e.g. carbonization). For example, such a thermal treatment is accomplished using a ramp of temperature and a gas optimised to achieve high electronic conductivity. For example, the ramp starts at a temperature close to room temperature and increases gradually (e.g. at a 3-10° C./min rate, preferably at a 5° C./min rate) up to a temperature of at least 200° C. In one example, the temperature reaches a first plateau and remains at this temperature for a period of 30 minutes to 2 hours (preferably about 1 hour) and then increases again gradually to reach a temperature of at least 500° C., or at least 600° C.

(17) Any inert gas (argon, nitrogen, etc.) may be used. In one example, an argon/carbon dioxide mixture was used during carbonization and achieved high electronic conductivity. For instance, the gas can be an Ar/CO.sub.2 mixture having a volume ratio of about 60:40 to about 90:10, or about 70:30 to about 80:20, or about 75:25.

(18) The use of PAN as a polymer allows for the formation of an activated carbon layer (see Okada, K. et al., Chem. Comm., 2011, 47 (26), 7422-7424). The presence of the activated carbon layer improves the electronic conductivity (electron transfer at the interface) and the interfacial stability of the material (see also Ding, Z. et al., Phys. Chem. & Chem. Phys., 2011, 13 (33), 15127-15133).

(19) For example, the coated particles are characterized by SEM and/or by measuring the powder's electronic conductivity. FIG. 2 shows the SEM images for one embodiment of the present application and demonstrate that the coating on LTO primary particles prepared by the present method is homogeneous. The carbon layer on the surface of the particles can also be observed by transmission electronic microscopy (TEM). The thickness of the carbon layer on the surface of the particles is below 20 nm, or below 10 nm, or even below 5 nm. For instance, FIG. 3 shows a thickness of an amorphous carbon layer of around 1.0-1.5 nm.

(20) In order to demonstrate the method's effectiveness to fill the active material pores with carbon, TEM images of the cross-section of a C-coated LTO particle (FIG. 4) were obtained. FIG. 4a shows the cross-section of a particles made by focused ion-beam etching (FIBE). Nickel nanoparticles located inside the activated carbon in FIG. 4a are a consequence of the FIBE procedure. On the images, the smallest pores (4c and d) are filled with carbon (arrows) and the biggest pores have a coating of 0.5-1.5 nm on the surface (4a and b) as determined by energy dispersive spectroscopy (EDS). The filling of the pores by carbon enhances the electronic conductivity and allows for more efficient charge and discharge at high cycling rate (10C and more).

(21) Moreover, one of the characteristics of the activated carbon coating is the nitrogen/carbon (N/C) ratio. An activated carbon coating formed by the carbonization of PAN is composed of fused aromatic rings comprising nitrogen and carbon atoms (nitrogen-containing polyaromatic structure, i.e. a graphene-like structure). In one embodiment, the coating is composed of about 4 wt. % to about 15 wt. %, or about 6 wt. % to about 11 wt. %, of nitrogen, the rest being carbon. The nitrogen content is dependent, for instance, on the final carbonization temperature; a higher temperature is generally associated with a lower amount of nitrogen (see Rahaman, M. S. A. et al.). Also, the surface area of the coated particles is between about 2 m.sup.2/g and about 20 m.sup.2/g, or between about 4 m.sup.2/g and about 15 m.sup.2/g, or between about 6 m.sup.2/g and about 10 m.sup.2/g, as determined by Brunauer-Emmett-Teller (BET) surface area analysis. The surface area can be adjusted as a function of the molecular weight (M.sub.n) of the poly(acrylonitrile), where a M.sub.n for the polymer leading to a surface area around 8 m.sup.2/g is preferred.

(22) Electronic conductivity will be as low as 10.sup.−9 S/cm for an organic content below 1.0 wt %. In an exemplified embodiment, conductivity was measured on the compressed powder. For organic content equal or higher than 1.5 wt %, the conductivity can be even higher than 10.sup.−4 S/cm, due to the presence of free aggregation of carbon in the samples. The aggregation allows for a good contact between the particles but may reduce, in certain cases, the diffusion of lithium. For instance, an optimal total organic content could be between about 0.5 and about 1.5 wt % as determined by thermogravimetric analysis (TGA) analysis under helium.

(23) The carbon produced by the present method is amorphous as determined by RAMAN spectroscopy and shows a ratio D/G between 2 and 3.5.

(24) For the preparation of an electrode comprising the coated particles, either for experimental analysis or as part of an electrochemical cell, the carbon-coated active particles are casted on a support, i.e. a current collector. In one example, the coated active particles are mixed with a binder and coated on the collector, for instance, as a slurry including also a solvent, which is dried after casting. The binder is selected taking into account the compatibility with the electrochemically active material, the current collector, the electrolyte, and other parts of the electrochemical cell which could be in contact with the binder. For instance, the binder may be a water-soluble polymer binder or a non-aqueous polymer binder.

(25) Examples of binders include SBR (styrene butadiene rubber) optionally with a thickening agent such as CMC (carbomethoxy cellulose), PAA (poly(acrylic acid)), PMMA (poly(methacrylic acid)), or a combination thereof, but also other known polymer binders. Examples of polymer binders may also include fluorinated polymers like polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE). Other examples of binders include aqueous base binders like SBR (Styrene Butadiene Rubber), NBR (butadiene acrylonitrile rubber), HNBR (hydrogenated NBR), CHR (epichlorohydrin rubber), ACM (acrylate rubber), and the like. These may be combined with CMC or an acidic polymer like PAA or PMAA. The mixture to be coated optionally includes additional components like inorganic particles, ceramics, salts (e.g. lithium salts), conductive materials, and the like. In a preferred embodiment, no additional carbon source is added to the slurry before coating on the current collector.

(26) The electrode produced by the present process is for use in the assembly of an electrochemical cell further comprising an electrolyte and a counter-electrode. The material composing the counter-electrode is selected as a function of the material used in the electrode. The electrolyte may be a liquid, gel or solid polymer electrolyte and comprises a lithium salt and/or is conductive to lithium ions.

EXAMPLES

(27) The following non-limiting examples are illustrative embodiments and should not be construed as limiting the scope of the present application. These examples will be better understood with reference to the accompanying figures.

Example 1: Carbon Coating Process

(28) a) Emulsion Formation and Polymerization

(29) LTO was used in the present example, but could be replaced by any other electrochemically active material. 20 g of LTO were introduced in a 250 mL round bottom flask and stirred by magnetic agitation. Then 100 mL of nanopure water were added to the active material in the flask. The slurry obtained was sonicated at a power of 70% for 6 min. After sonication, the slurry was cooled in an ice bath. A solution of 3 g of acrylonitrile and 25 mg of AIBN was added to the flask. The resulting slurry (13% wt of monomer) was sonicated for another 6 min at the same power. The slurry was then degassed for 30 min using a stream of nitrogen. The slurry was then heated to 70° C. for 12 hours with high stirring under nitrogen.

(30) b) Spray Drying

(31) The slurry obtained in step (a) was heated to 180° C. After heating, the slurry was dried by spray-drying using a pump at 25% and a blower at 95-100%, percentages of the apparatus' full power.

(32) c) Carbonization

(33) The slurry was carbonized under air using a temperature ramp of from 25° C. to 240° C. at a rate of 5° C./min, and further kept at 240° C. for 1 hour. Then the temperature was raised to 700° C. with a rate of 5° C./min under an atmosphere of Argon:CO.sub.2 (75:25) or nitrogen.

Example 2: Carbon-Coated LTO (C-LTO) Electrode Production

(34) The carbon-coated LTO material prepared by the process of Example 1 was mixed with Styrene-Butadiene Rubber (SBR) binder (48% water solution) and PAA (250 000-500 000 g/mol) to form a slurry. The solid ratio of C-LTO/SBR/PAA was 96.0/2.5/1.5 (for a dry content in carbon from the coating of 1.0 wt %). The resulting slurry was coated on an aluminum foil with a thickness of 15 microns.

(35) As a reference electrode, the LTO material without any carbon coating was mixed with conductive carbon agent, SBR (48% water solution) and Carboxymethyl cellulose (CMC, 1.5% water solution), at a LTO/carbon/SBR/CMC solid weight ratio of 91.0/5.0/2.5/1.5. The resulting slurry was coated on an aluminum foil having a 15 microns thickness.

(36) For comparison purposes, commercially available carbon-coated LTO was mixed with a conductive carbon agent, SBR (48% water solution) and CMC (1.5% water solution), at a LTO/carbon/SBR/CMC solid weight ratio of 91.0/5.0/2.5/1.5. The resulting slurry was casted on a 15 microns thick aluminum foil.

Example 3: Lithium C-LTO Half Cells and LFP-C-LTO Full Cells Production

(37) Coin half and full cells were produced using the three electrodes of Example 2 in order to evaluate their electrochemical properties.

(38) a) Lithium C-LTO Half Cells

(39) Lithium half cells were produced using lithium metal as counter electrode and the C-LTO and reference electrodes as working electrodes. The cells were produced using polyethylene (PE) separators, having a thickness of 16 microns, to separate the LTO electrode and the lithium metal electrode. An electrolyte was prepared with 1.3 mol/kg of LiPF.sub.6 and a mixture of propylene carbonate (PC), dimethyl carbonate (DMC), and ethyl methyl carbonate (EMC) as solvent, with a ratio PC/DMC/EMC of 4/3/3. Each cell was provided with 150 μL of the resulting electrolyte.

(40) b) LFP-C-LTO Full Cells

(41) Lithium iron phosphate, LiFePO.sub.4 (LFP) was mixed with conductive carbon agent and polyvinylidene difluoride (PVdF, 6% N-Methyl-2-pyrrolidone solution), with a solid ratio LFP/carbon/PVdF of 95.0/5.0/5.0. The resulting slurry was coated on an aluminum foil with a thickness of 15 microns.

(42) Full cells were produced using LFP electrode as cathode and the LTO electrode as anodes for each of the LTO electrodes of example 2. The same PE separator and LiPF.sub.6—PC/DMC/EMC electrolyte than for the lithium C-LTO half cells were used.

Example 4: Electrochemical Properties

(43) a) Characterization of Lithium Half Cells

(44) Electrochemical capacities of the C-LTO and the reference electrodes were measured in lithium half cells to obtain the results shown in Table 1 below.

(45) TABLE-US-00001 TABLE 1 Charge (Ch) and Discharge (Dis) capacities and efficiencies Ch. Dis. Ch./Dis. Capacity Capacity Efficiency Cycle (mAh/g) (mAh/g) (%) Reference Formation 166.7 163.8 98.3 (SBR/CMC) 0.3 mA Nominal Ch./ 164.0 163.3 99.6 Dis. 0.6 mA C-LTO Formation 171.7 163.1 95.0 1.0 wt. % 0.3 mA (SBR/PAA) Nominal Ch./ 163.5 162.1 99.2 Dis. 0.6 mA

(46) Charge/discharge cycling tests were performed using a Toyo battery test system (TOSCAT-3100™). For the first charge/discharge cycle, a 0.3 mA current was applied. Charge was performed in constant current/constant voltage (CC-CV) mode, with a maximum voltage of 1.0 V and a cut-off current of 0.03 mA. Discharge was performed in CC mode down to 2.7 V. For the second cycle, 0.6 mA was applied for both charge and discharge steps. FIG. 5 presents the charge and discharge curves for both the C-LTO and the lithium half cell reference, showing that the C-LTO electrode displayed a reduced voltage drop (or IR drop) when compared to the result obtained with the reference electrode. As the internal resistance was lower for the C-LTO electrode, the carbon coating prepared by the present method would increase the conductivity between particles to reduce the internal resistance for the C-LTO electrode.

(47) b) Charges/Discharge Curves of LFP-LTO Full Cells

(48) Charge and discharge test was performed with LFP-LTO full cells. For the first charge/discharge cycle, a 0.3 mA current was applied. Charge was done in constant current/constant voltage (CC-CV) mode, with a maximum voltage of 2.4 V and a cut-off current was 0.03 mA. Discharge was done in CC mode down to 0.5 V. For the second cycle, 0.6 mA were applied for both charge and discharge steps.

(49) Alternative current (AC) impedance was measured to evaluate the resistance of the LTO electrodes. The test was performed using a research-grade multi-channel potentiostat (Biologic VMP3®), using a frequency between 1 MHz-10 mHz and AC amplitude of 10 mV.

(50) FIG. 6 illustrates the charge and discharge curves for full cells using the C-LTO electrode or the reference electrode as anode. The curves show a steeper change occurring at the end of the charging and discharging tests of the C-LTO electrode. This confirms an improvement in lithium ion diffusion in the C-LTO electrode compared to the reference electrode.

(51) c) Electrochemical Impedance of Lithium Half Cells and LFP-LTO Full Cells

(52) The electrochemical impedance for both the C-LTO and the reference electrodes was tested in LFP-LTO full cells (FIG. 7a) and lithium half cells (FIG. 7b). FIG. 7 presents the Nyquist plots measured at 25° C. at state of charge (SOC)=50%, meaning that 50% of the capacity was charged.

(53) According to FIG. 7, the C-LTO electrode showed less reaction resistance for charge and discharge reaction when compared to the reference electrode.

(54) d) Charge and Discharge Capacities of LFP-LTO Full Cells

(55) Electrochemical capacities of the reference electrode, the commercial carbon-coated electrode and C-LTO electrode were measured in LFP-LTO full cells as shown in Table 2 below.

(56) TABLE-US-00002 TABLE 2 Charge and Discharge capacities 0.2 C 1 C 2 C 4 C 10 C Reference Charge 100 91.9 86.9 78.9 27.4 (SBR/CMC) Discharge 100 94.1 90.3 84.6 71.7 Commercial C-LTO Charge 100 95.8 90.2 79.8 17.2 (SBR/CMC) Discharge 100 97.5 94.5 87.9 70.9 C-LTO 1.0 wt. % Charge 100 96.3 91.4 85 63.5 (SBR/PAA) Discharge 100 95.5 93.4 81.2 80.0

(57) Load tests were performed to analyse the fast charging and discharging properties for the LFP-LTO full cells. Full cells with C-LTO electrode, reference electrodes and commercial electrodes were charged and discharged at 1C, 2C, 4C, and 10C. FIG. 8 shows that a 1C current can charge or discharge the full capacity of the cell in 1 hour, while times for 2C, 4C and 10C are respectively 30, 15 and 6 minutes.

(58) For the charge load test, after the full discharge at 0.2C, the LFP-LTO full cells were charged at 1C, and then charged again at 0.2C. Then the full cells were discharged at 0.2C and charged at 2C.

(59) For the discharge load test, after the full charge at 0.2C, the LFP-LTO full cells were discharged at 1C, and then discharged again at 0.2C. Then the full cells were charged at 0.2C and discharged at 2C.

(60) The capacity retention at xC was calculated using Equation 1 below.
Capacity retention=(Capacity at xC)/(Capacity at 0.2C)×100  Equation 1

(61) The capacity in the CC region was used for the calculation of charge load characteristics.

(62) According to FIG. 8, the C-LTO electrode showed a better capacity retention at 10C for both the charging (FIG. 8a) and discharging (FIG. 8b) tests.

(63) e) Direct Current Internal Resistance (DCIR) of LFP-LTO Full Cells

(64) DCIR was calculated using Equation 2 below.

(65) $\begin{array}{cc}\mathrm{DCIR}=\frac{\left[V_{\mathrm{SOC}50\%\left(\mathrm{xC}\right)}-V_{\mathrm{SOC}50\%\left(0.2C\right)}\right]}{\left[\left(\mathrm{Current}\mathrm{of}\mathrm{xC}\right)-\left(\mathrm{Current}\mathrm{of}0.2C\right)\right]}& \mathrm{Equation}2\end{array}$

(66) Where V.sub.SOC50% (xc) is the voltage at SOC50% measured at xC, and V.sub.SOC50%(0.2C) is the voltage at SOC50% measured at 0.2C.

(67) DCIR for the reference, the commercial carbon-coated and the C-LTO electrodes were calculated and the results are shown in Table 3 below.

(68) TABLE-US-00003 TABLE 3 Charge and Discharge DCIR Charge DCR/ohm Discharge DCR/ohm Reference (SBR/CMC) 25.5 31.0 Commercial C-LTO (SBR/CMC) 27.3 33.4 C-LTO 1.0 wt. % (SBR/PAA) 18.9 21.5

(69) FIG. 9 shows the charge and discharge mean value of DCIR for 2C and 4C. According to FIG. 9, the C-LTO electrode showed a 30-35% lower internal resistance than the reference electrode or the commercial carbon-coated LTO electrode. Therefore, in light of the above example, it appears that carbon-coated LTO electrodes such as described herein show improved electrochemical performances compared to the conventional LTO electrodes, or even commercially available carbon-coated LTO electrodes. The thin carbon coating allows for better conductivity, enhanced lithium diffusion and improved capacity retention at high current (10C), but also provides a lower internal resistance or charge/discharge reaction resistance.

(70) Numerous modifications could be made to any of the embodiments described above without departing from the scope of the present invention. Any references, patents or scientific literature documents referred to in this application are incorporated herein by reference in their entirety for all purposes.