CARBON-BOUND LITHIUM-ION CONDUCTOR-CARBON COMPOSITE CATHODE MATERIAL HAVING CARBON FIBER STRUCTURE AND FABRICATION METHOD THEREFOR
20210384507 · 2021-12-09
Inventors
- Wanfang HE (Hangzhou, Zhejiang, CN)
- Weitao WANG (Hangzhou, Zhejiang, CN)
- Jie YANG (Hangzhou, Zhejiang, CN)
Cpc classification
H01M4/133
ELECTRICITY
H01M4/1393
ELECTRICITY
D01F9/12
TEXTILES; PAPER
Y02E60/10
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
H01M2004/021
ELECTRICITY
H01M4/58
ELECTRICITY
H01M10/0525
ELECTRICITY
International classification
H01M10/0525
ELECTRICITY
Abstract
A method for fabricating a carbon-bound lithium-ion conductor-carbon composite cathode material having a carbon fiber structure, comprising: mixing a carbon material, a lithium-ion conductor, an organic polymer material and an organic solvent, thereby obtaining a mixed slurry A; granulating and drying the mixed slurry A to obtain solid particles M; performing a high-temperature carbonization treatment on the solid particles M in an inert atmosphere, thereby obtaining a carbon-bound lithium-ion conductor-carbon composite cathode material having a carbon fiber structure.
Claims
1. A method for fabricating a carbon-bound lithium-ion conductor-carbon composite cathode material having a carbon fiber structure, comprising: Step 1: mixing a carbon material, a lithium-ion conductor, an organic polymer material and an organic solvent, thereby obtaining a mixed slurry A; Step 2: granulating and drying the mixed slurry A to obtain solid particles M; Step 3: performing a high-temperature carbonization treatment on the solid particles M in an inert atmosphere, thereby obtaining a carbon-bound lithium-ion conductor-carbon composite cathode material having a carbon fiber structure.
2. The method for fabricating a carbon-bound lithium-ion conductor-carbon composite cathode material having a carbon fiber structure of claim 1, wherein the carbon material is selected from at least one of the following: graphite, soft carbon and hard carbon.
3. The method for fabricating a carbon-bound lithium-ion conductor-carbon composite cathode material having a carbon fiber structure of claim 1, wherein the lithium-ion conductor is a metal ion compound.
4. The method for fabricating a carbon-bound lithium-ion conductor-carbon composite cathode material having a carbon fiber structure of claim 3, wherein the metal ion compound comprise one or more corresponding ion compounds of the metals excluding Mn, Fe, Co, Ni, Cu, Au, Ag, Zn, Cd, Cr, Cd, Hg, Ge, Pb, Ru, Rh, Pd, Os, Ir and Pt.
5. The method for fabricating a carbon-bound lithium-ion conductor-carbon composite cathode material having a carbon fiber structure of claim 1, wherein the lithium-ion conductor is selected from at least one of the following: a lithium-ion metal oxide, a lithium-ion metal composite oxide, a lithium-ion metal sulfide, a lithium-ion metal nitride, a lithium-ion metal fluoride, a lithium-ion metal carbide, a lithium-ion metal selenide, a lithium-ion metal telluride, a lithium-ion metal phosphate, Li.sub.2CO.sub.3, Li.sub.2TiO.sub.3, Li.sub.4Ti.sub.5O.sub.12, Li.sub.2ZrO.sub.3, LiVO.sub.3, Li.sub.3VO.sub.4, LiNbO.sub.3, Li.sub.3NbO.sub.4, and Li.sub.3Ln.sub.3M.sub.2O.sub.12, wherein M is selected from Te or W, wherein Ln is selected from Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu.
6. The method for fabricating a carbon-bound lithium-ion conductor-carbon composite cathode material having a carbon fiber structure of claim 5, wherein the metal nitride is selected from at least one of the following: Li.sub.3N, Li.sub.3N—LiCl, Li.sub.9N.sub.2Cl, Li.sub.3AlN.sub.2, LiSi.sub.2N.sub.3, and Li.sub.0.85Ca.sub.0.075Si.sub.2N.
7. The method for fabricating a carbon-bound lithium-ion conductor-carbon composite cathode material having a carbon fiber structure of claim 6, wherein the metal phosphate in the lithium-ion conductor is selected from at least one of the following: Li.sub.3PO.sub.4, LiMPO.sub.4, LiM.sub.2(PO.sub.4).sub.3, Li.sub.1-xM.sub.xTi.sub.2-x(PO.sub.4).sub.3, wherein M is selected from at least one of the following: Mg.sup.2+, Ca.sup.2+, Sr.sup.2+, Ba.sup.2+, Ge, Ti, Hf, Al, Sc, Y and La.
8. The method for fabricating a carbon-bound lithium-ion conductor-carbon composite cathode material having a carbon fiber structure of claim 1, wherein the weight ratio of the lithium-ion conductor to the carbon material in step 1 is 1:2-1:100.
9. The method for fabricating a carbon-bound lithium-ion conductor-carbon composite cathode material having a carbon fiber structure of claim 1, wherein the organic polymer material in step 1 is an organic polymer material capable of being converted into carbon fiber after high-temperature carbonization.
10. The method for fabricating a carbon-bound lithium-ion conductor-carbon composite cathode material having a carbon fiber structure of claim 1, wherein the organic polymer material in step 1 is selected from one of the following: polyacrylonitrile, phenolic resin and asphalt.
11. The method for fabricating a carbon-bound lithium-ion conductor-carbon composite cathode material having a carbon fiber structure of claim 1, wherein the weight of the organic polymer material in step 1 accounts for 1%-30% of the total weight of the rest of materials excluding the solvent.
12. The method for fabricating a carbon-bound lithium-ion conductor-carbon composite cathode material having a carbon fiber structure of claim 1, wherein the organic solvent in step S1 is a liquid organic substance capable of dissolving the target polymer material.
13. The method for fabricating a carbon-bound lithium-ion conductor-carbon composite cathode material having a carbon fiber structure of claim 1, wherein the organic solvent capable of dissolving polyacrylonitrile is selected from at least one of the following: dimethylformamide (DMF), N, N-dimethylacetamide (DMAc) and dimethyl sulfoxide (DMSO).
14. The method for fabricating a carbon-bound lithium-ion conductor-carbon composite cathode material having a carbon fiber structure of claim 1, wherein the organic solvent capable of dissolving phenolic resin is selected from at least one of the following: methanol, ethanol and propanol.
15. The method for fabricating a carbon-bound lithium-ion conductor-carbon composite cathode material having a carbon fiber structure of claim 1, wherein the organic solvent capable of dissolving asphalt is selected from at least one of the following: liquid hydrocarbon solvents such as gasoline and diesel.
16. The method for fabricating a carbon-bound lithium-ion conductor-carbon composite cathode material having a carbon fiber structure of claim 1, wherein the carbonization treatment temperature of the material in step 3 ranges from 400-1500° C.
17. The method for fabricating a carbon-bound lithium-ion conductor-carbon composite cathode material having a carbon fiber structure of claim 1, wherein the carbonization treatment duration of the material in step 3 ranges from 1-50 hours.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0031]
[0032]
[0033]
[0034]
[0035]
[0036]
[0037]
[0038]
[0039]
DETAILED DESCRIPTION
[0040] Drawings and detailed embodiments are combined hereinafter to further elaborate the method for fabricating a carbon-bound lithium-ion conductor-carbon composite cathode material having a carbon fiber structure of the present disclosure.
Embodiment 1
[0041] For a comparison, in this embodiment, a pure mesophase microsphere material is adopted to fabricate a half-cell for testing.
[0042] The process of fabricating a cell, comprising: weighing 0.8000 g of mesophase carbon microspheres (N.sub.7), adding 0.1003 g of conductive carbon black and 3.3333 g of NMP solution containing 3.0% PVDF, thereby making the mass ratio of N.sub.7 to conductive carbon black to PVDF be 8:1:1; subsequently, ball-milling for 30 minutes to obtain a slurry, and coating the slurry on a copper foil to obtain an electrode piece having a thickness of 90 μm; drying in a furnace in a nitrogen atmosphere at a temperature of 120° C. for 3 hours, and making the electrode piece into a half-cell in a glove box; weighing a small round piece and placing it into an anode shell; subsequently, placing a diaphragm, feeding 60 μl of electrolyte solution, and sequentially placing a metal lithium piece, a gasket, an elastic piece and a cathode shell; finally, hydraulically packaging using a hydraulic machine, thereby obtaining a button cell.
[0043] The process of testing the cell, comprising: respectively testing the obtained button cell at a current density of 100, 200, 300, 400, 500 and 600 mA/g under a voltage ranging from 0.01V to 2.00V, and measuring the gram capacity at different current densities, thus obtaining the results shown in
[0044] The test results of the pure mesophase carbon microsphere material in embodiment 1 show that the gram capacity of the material greatly decreases when the current density increases: when the current density is 300 mA/g, the capacity is 150 mAh/g, and when the current density increases to 400 mA/g, the capacity decreases to 90 mAh/g.
Embodiment 2
[0045] In this embodiment, phenolic resin is adopted in the method for fabricating a carbon-bound ZrO.sub.2/MgO-carbon composite cathode material having a carbon fiber structure, and the fabricated material is made into a button cell for testing.
[0046] A method for fabricating the material, comprising the steps of:
[0047] First, weighing 1324.00 g of absolute ethyl alcohol, then adding 25.91 g of ZrO.sub.2, 16.94 g of MgO and 385.65 g of mesophase carbon microspheres having an average particle size of 20 μm, thereby making the mass ratio of metal oxide to carbon be 1:9; subsequently, adding 64.27 g of an ethanol solution containing 20 wt % of phenolic resin, and making the phenolic resin account for 3% of the total amount of ZrO.sub.2, MgO and carbon; ball-milling, mixing and discharging, thereby obtaining a mixed slurry.
[0048] Second, spray-drying at a temperature of 100° C. to obtain a solid powder.
[0049] Third, taking 5.0012 g of the solid powder and feeding it into a tube furnace; subsequently, sintering at a temperature of 800° C. for 5 hours in a nitrogen atmosphere, thus obtaining a carbon-bound ZrO.sub.2/MgO-carbon composite cathode material having a carbon fiber structure by using phenolic resin.
[0050] The process of fabricating a cell, comprising: weighing the composite cathode material, the conductive carbon black and the PVDF according to a mass ratio of 94:3:3; adding the NMP, thus enabling the solid content to reach 24%; mixing in a vacuum mixer for 20 minutes, and then coating on the surface of a copper foil, wherein the coating thickness is 120 μm; drying in a drying cabinet at a temperature of 90° C. for 30 minutes, and then conducting roll-pressing and slicing; subsequently, placing into a vacuum drying chamber and drying at a temperature of 90° C. for 12 hours; making the electrode piece into a half-cell in a glove box; weighing a small round piece and placing it into an anode shell; subsequently, placing a diaphragm, feeding 60 μl of electrolyte solution, and sequentially placing a metal lithium piece, a gasket, an elastic piece and a cathode shell; finally, hydraulically packaging using a hydraulic machine, thereby obtaining a button cell.
[0051] The process of testing the cell, comprising: charging and discharging the button cell using a constant current for one cycle at a current density of 33 mA/g, and then respectively charging and discharging the cell at a current density of 100 mA/g, 200 mA/g, 300 mA/g, 400 mA/g, 500 mA/g, 600 mA/g, 700 mA/g, 800 mA/g, 900 mA/g and 1000 mA/g for 10 cycles; finally, charging and discharging the cell at a current density of 100 mA/g for 10 cycles, thus obtaining the results shown in
[0052] It can be seen from
Embodiment 3
[0053] In this embodiment, polyacrylonitrile is adopted in the method for fabricating a carbon-bound ZrO.sub.2/CaO-carbon composite cathode material having a carbon fiber structure, and the fabricated material is made into a button cell for testing.
[0054] A method for fabricating the material, comprising the steps of:
[0055] First, weighing 100.00 g of water, then adding 21.54 g of ZrO.sub.2 and 20.01 g of CaCO.sub.3, thus making the molar ratio of Zr:Ca be 1:2; subsequently, adding 12.52 g of polyethylene glycol (PEG), and making the PEG account for 30% of the total amount of ZrO.sub.2 and CaCO.sub.3; ball-milling in a ball mill at a speed of 250 r/min for 10 hours, discharging, and adding 120.0 mL of water to wash; spray-drying at a temperature of 120° C. to obtain a white powder; taking 25.00 g of the white powder and feeding it into a tube furnace in an air atmosphere; sintering at a temperature of 1000° C. for 7 hours, grinding the sample powder and screening using an 80-mesh sieve.
[0056] Second, weighing 6.96 g of the obtained sample powder, adding 10.0 mL of NMP solution and 27.84 g of carbon (N.sub.7), thus making the mass ratio of the inorganic substance to carbon be 2:8; subsequently, adding 34.8 g of NMP solution containing 5 wt. % of polyacrylonitrile, and making the polyacrylonitrile account for 5% of the total amount of the inorganic substance and the carbon; finally, adding 20.0 mL of NMP solution and ball-milling, thereby obtaining a mixed slurry.
[0057] Third, drying the mixed slurry using a spray dryer at a temperature of 150° C., thereby obtaining a solid powder.
[0058] Fourth, feeding the solid powder into a tube furnace, and sintering at a temperature of 1000° C. in a nitrogen atmosphere for 5 hours, thus obtaining a carbon-bound ZrO.sub.2/CaO-carbon composite cathode material having a carbon fiber structure by using polyacrylonitrile.
[0059] In this embodiment, the process of fabricating and testing the cell is the same as that in embodiment 2. As shown in
Embodiment 4
[0060] In this embodiment, polyacrylonitrile is adopted in the method for fabricating a carbon-bound TiO.sub.2/MgO/CaO-carbon composite cathode material having a carbon fiber structure, and the fabricated material is made into a button cell for testing.
[0061] A method for fabricating the material, comprising the steps of:
[0062] First, weighing 100.00 g of water, then adding 15.92 g of TiO.sub.2, 10.47 g of MgO, 5.642 g of CaO and 9.61 g of PEG, and making PEG accounts for 30% of the total amount of TiO.sub.2, MgO and CaO; ball-milling and spray-drying at a temperature of 120° C. to obtain a white powder; taking 25.07 g of the white powder and feeding it into a tube furnace in an air atmosphere; sintering at a temperature of 1350° C. for 7 hours, grinding the sample powder and screening using an 80-mesh sieve.
[0063] Second, weighing 6.78 g of the obtained sample powder, adding 10.0 mL of NMP solution, ball-milling, and then adding 12.59 g of carbon (N.sub.7), thus making the mass ratio of the inorganic substance to carbon be 3.5:6.5; subsequently, adding 30.99 g of NMP solution containing 5 wt. % of polyacrylonitrile, and making the polyacrylonitrile account for 5% of the total amount of the inorganic substance and carbon; finally, adding 30.0 mL of NMP solution and ball-milling, thereby obtaining a mixed slurry.
[0064] Third, spray-drying the mixed slurry to obtain a solid powder.
[0065] Fourth, feeding the solid powder into a tube furnace, and sintering at a temperature of 900° C. in a nitrogen atmosphere for 5 hours, thus obtaining a carbon-bound TiO.sub.2/MgO/CaO-carbon composite cathode material having a carbon fiber structure by using polyacrylonitrile.
[0066] In this embodiment, the process of fabricating and testing the cell is the same as that in embodiment 2. As shown in
Embodiment 5
[0067] In this embodiment, phenolic resin is adopted in the method for fabricating a carbon-bound TiO.sub.2/Li.sub.2O-carbon composite cathode material having a carbon fiber structure, and the fabricated material is made into a button cell for testing.
[0068] A method for fabricating the material, comprising the steps of:
[0069] First, respectively weighing 2.0498 g of LiOH.H.sub.2O and 1.9509 g of TiO.sub.2 according to a molar ratio of 2:1; subsequently, weighing 6.0040 g of flake graphite (HC-7), 30.99 g of an ethanol solution containing 5 wt % of phenolic resin, measuring out 40.0 ml of ethyl alcohol, and feeding them into a ball-milling tank; after ball-milling for 6 hours at a speed of 180 r/min, discharging the mixture, thus obtaining a mixed slurry.
[0070] Second, spray-drying the mixed slurry to obtain a solid powder.
[0071] Third, feeding the obtained solid powder into a high-temperature tube furnace at a temperature of 850° C. for 4 hours in an argon atmosphere, thus obtaining a carbon-bound TiO.sub.2/Li.sub.2O-carbon composite cathode material having a carbon fiber structure by using phenolic resin.
[0072] In this embodiment, the process of fabricating and testing the cell is the same as that in embodiment 2. As shown in
Embodiment 6
[0073] In this embodiment, phenolic resin is adopted in the method for fabricating a carbon-bound ZrO.sub.2/Y.sub.2O.sub.3-carbon composite cathode material having a carbon fiber structure, and the fabricated material is made into a button cell for testing.
[0074] A method for fabricating the material, comprising the steps of:
[0075] First, weighing 1310.90 g of absolute ethyl alcohol, 42.8559 g of ZrO.sub.2 and 1.2856 g of Y.sub.2O.sub.3, stirring for 5 minutes, and sanding for 15 minutes at a speed of 2500 r/min in a sanding mill; subsequently, adding 397.22 g of carbon (FSN) and 66.25 g of absolute ethyl alcohol solution containing 20 wt. % of phenolic resin, sanding at a speed of 2500 r/min for 10 minutes, and discharging the mixture to obtain a mixed slurry.
[0076] Second, spray-drying the mixed slurry at a temperature of 100° C. to obtain a solid powder.
[0077] Third, feeding the obtained solid powder into a high-temperature tube furnace, sintering at a temperature of 800° C. for 5 hours in a nitrogen atmosphere, thus obtaining a carbon-bound ZrO.sub.2/Y.sub.2O.sub.3-carbon composite cathode material having a carbon fiber structure by using phenolic resin.
[0078] In this embodiment, the process of fabricating and testing the cell is the same as that in embodiment 2. As shown in
Embodiment 7
[0079] In this embodiment, phenolic resin is adopted in the method for fabricating a carbon-bound TiO.sub.2/La.sub.2O.sub.3-carbon composite cathode material having a carbon fiber structure, and the fabricated material is made into a button cell for testing.
[0080] A method for fabricating the material, comprising the steps of:
[0081] First, weighing 1335.06 g of absolute ethyl alcohol, 42.8556 g of TiO.sub.2 and 2.1436 g of La.sub.2O.sub.3, stirring for 5 minutes, and sanding for 15 minutes at a speed of 2500 r/min in a sanding mill; subsequently, adding 404.96 g of carbon (FSN) and 67.56 g of absolute ethyl alcohol solution containing 20 wt. % of phenolic resin, then ball-milling to obtain a mixed slurry.
[0082] Second, spray-drying the mixed slurry at a temperature of 100° C. using a spray dryer, thus obtaining a black powder.
[0083] Third, weighing 6.8952 g of the obtained black powder and feeding it into a high-temperature tube furnace, sintering at a temperature of 800° C. for 5 hours in a nitrogen atmosphere, thus obtaining a carbon-bound TiO.sub.2/La.sub.2O.sub.3-carbon composite cathode material having a carbon fiber structure by using phenolic resin.
[0084] In this embodiment, the process of fabricating and testing the cell is the same as that in embodiment 2. As shown in
Embodiment 8
[0085] In this embodiment, phenolic resin is adopted in the method for fabricating a carbon-bound Li.sub.3PO.sub.4-carbon composite cathode material having a carbon fiber structure, and the fabricated material is made into a button cell for testing.
[0086] A method for fabricating the material, comprising the steps of:
[0087] First, weighing 900.05 g of absolute ethyl alcohol, adding 30.06 g of lithium phosphate, stirring for 5 minutes, and sanding for 15 minutes at a speed of 2500 r/min; subsequently, adding 270.05 g of carbon (FSN) and making the mass ratio of lithium phosphate to carbon be 1:9; adding 45.06 g of 20 wt. % phenolic resin and making phenolic resin account for 3% of the total amount of lithium phosphate and carbon; finally, sanding for 10 minutes at a speed of 2500 r/min, discharging and obtaining a mixed slurry.
[0088] Second, spray-drying the mixed slurry at a temperature of 100° C. using a spray dryer, thus obtaining a solid powder.
[0089] Third, weighing 8.6043 g of the solid powder and feeding it into a high-temperature tube furnace, sintering at a temperature of 800° C. for 5 hours in a nitrogen atmosphere, thus obtaining a carbon-bound Li.sub.3PO.sub.4-carbon composite cathode material having a carbon fiber structure by using phenolic resin.
[0090] In this embodiment, the process of fabricating and testing of the cell is the same as that in embodiment 2. As shown in
[0091] The rate cycling diagram of the cathode materials obtained in embodiment 1-8 are respectively tested at a current density of 100, 200, 300, 400, 500 and 600 mA/g in a voltage ranging from 0.01V-2.00V, and the test results are shown in Table 1.
TABLE-US-00001 TABLE 1 Capacity at 300 mA/g Capacity at 400 mA/g Sample No. (unit: mAh/g) (unit: mAh/g) Embodiment 1 150 90 Embodiment 2 255 240 Embodiment 3 251 220 Embodiment 4 220 160 Embodiment 5 345 335 Embodiment 6 260 230 Embodiment 7 290 280 Embodiment 8 281 275
[0092] According to the data shown in Table 1 and
[0093] The aforesaid description of the disclosed embodiments enables those skilled in the art to realize or use the present disclosure. The aforesaid embodiments may be modified or combined by those skilled in the art according to actual needs without departing from the spirit of the present disclosure. Therefore, the scope of the present disclosure is defined by the claims of the present disclosure.