CN101814599B - Novel carbon cathode material of power lithium ion cell and preparation method thereof - Google Patents
Novel carbon cathode material of power lithium ion cell and preparation method thereof Download PDFInfo
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- CN101814599B CN101814599B CN201010168930XA CN201010168930A CN101814599B CN 101814599 B CN101814599 B CN 101814599B CN 201010168930X A CN201010168930X A CN 201010168930XA CN 201010168930 A CN201010168930 A CN 201010168930A CN 101814599 B CN101814599 B CN 101814599B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 75
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 24
- 239000010406 cathode material Substances 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000004793 Polystyrene Substances 0.000 claims abstract description 19
- 229920002223 polystyrene Polymers 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 27
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000012300 argon atmosphere Substances 0.000 claims description 16
- 238000004945 emulsification Methods 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- 239000007773 negative electrode material Substances 0.000 claims description 3
- 239000011324 bead Substances 0.000 abstract description 2
- RCHKEJKUUXXBSM-UHFFFAOYSA-N n-benzyl-2-(3-formylindol-1-yl)acetamide Chemical compound C12=CC=CC=C2C(C=O)=CN1CC(=O)NCC1=CC=CC=C1 RCHKEJKUUXXBSM-UHFFFAOYSA-N 0.000 abstract 1
- 238000005580 one pot reaction Methods 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 12
- 229910002804 graphite Inorganic materials 0.000 description 11
- 239000010439 graphite Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000009792 diffusion process Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000002847 impedance measurement Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- Y—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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a novel carbon cathode material of a power lithium ion cell and a preparation method thereof. By the adoption of the method, laminated array porous carbon is prepared by using polystyrene beads as a template and phenolic aldehyde resin as a carbon source by a one-pot method. By using the porous carbon as the cathode material, the cell has high multiplying power performance and circulation performance in high current density.
Description
Technical field
The present invention relates to the power lithium-ion battery field, particularly a kind of novel carbon cathode material of power lithium ion cell and preparation method thereof.
Background technology
Pure electric automobile and hybrid-electric car more and more receive people's attention at present, and wherein lithium ion battery is optimal electrical source of power.Graphite is as present business-like lithium ion battery negative material, low price, Heat stability is good, environmental friendliness; But the high rate performance of its relative mistake and low storage lithium ability have limited the development of lithium ion battery in the electric motor car industry.
The power and the energy density that how to improve lithium ion battery become current research focus.According to diffusion equation t=L
2/ 2D (t, L, D represent diffusion time, diffusion length, diffusion coefficient respectively) increases the diffusion coefficient of lithium ion in intercalation materials of li ions and reduces diffusion length, can improve the migration velocity of lithium ion, thereby improves the power density of lithium ion battery.
Summary of the invention
The objective of the invention is to overcome the shortcoming that exists in the prior art, the carbon negative electrode material of lithium ion cell of a kind of capacitance height, good rate capability is provided.
Another object of the present invention is to provide a kind of preparation method of above-mentioned novel carbon cathode material of power lithium ion cell.
The object of the invention is realized through following technical proposals:
A kind of preparation method of novel carbon cathode material of power lithium ion cell comprises the steps:
(1) sodium carbonate of the water of the formaldehyde of the resorcinol of 1.32～2.64 mass parts, 2.06～5 mass parts, 1.92～4 mass parts, 0.00636～0.013 mass parts is mixed and stirred 30～60 minutes, obtain mixed liquor;
(2) in said mixed liquor, add the polystyrene of 2～4 mass parts then, stirred 30～60 minutes, filter, obtain filter residue;
(3) said filter residue was reacted 36～72 hours under 70～85 ℃ of vacuum, obtain stratiform array porous carbon presoma;
(4) under argon atmosphere, 300～500 ℃ of calcinings in tube furnace of layered array porous carbon presoma were calcined 2～4 hours down for 1～2 hour, 900 ℃, cool to room temperature prepares carbon negative electrode material of lithium ion cell then.
In the step 2, said polystyrene is the polystyrene sphere that adopts the emulsion method polymerization to prepare, and concrete steps are: the styrene (26～30 mass parts) that 0.1～0.2 mol NaOH was handled; 0.5 the sodium peroxydisulfate of～1 mass parts; The deionized water of 240～350 mass parts, the polyvinylpyrrolidone of 1.8～2 mass parts (PVP), stirring reaction 24～30 hours under the nitrogen atmosphere in 70～80 ℃ of temperature ranges; With the sedimentation and filtration that obtains; Wash 1～2 time, dried 12～24 hours down for 60～70 ℃ then, obtain polystyrene sphere.
Principle of the present invention is following: being under the effect of template with the polystyrene sphere, is carbon source with phenolic resins, prepares stratiform array porous carbon through one kettle way.With this porous carbon is negative material, contrasts with business-like native graphite, finds that it has high rate performance and cycle performance preferably under high current density.
The present invention compared with prior art has following advantage and effect:
(1) the present invention adopts the synthesizing porous carbon of one kettle way, and is simple to operate, is easy to control.
(2) the present invention adopts template, forms the unique texture of stratiform array porous carbon, helps the migration of lithium ion and the transmission of electronics.
(3) the present invention compares with present business-like native graphite, and better high rate performance and cycle performance are arranged, and helps the development of carbon as the power lithium-ion battery negative material.
Description of drawings
Fig. 1 is SEM figure (a) and the high resolution graphics (b) of embodiment 1 stratiform array porous carbon.
Fig. 2 is the EDX figure of embodiment 1 stratiform array porous carbon.
Fig. 3 is the XRD figure of embodiment 1 stratiform array porous carbon.
Fig. 4 is the IR figure (a) of embodiment 1 stratiform array porous carbon presoma and the IR figure (b) of stratiform array porous carbon.
Fig. 5 is the TG～DSC figure of embodiment 1 stratiform array porous carbon presoma.
Fig. 6 is the isothermal nitrogen adsorption curve and the BJH pore size distribution curve figure of embodiment 1 stratiform array porous carbon.
Fig. 7 is that embodiment 1 stratiform array porous carbon (a) and Comparative Examples are already changed first three circle charging and discharging curve figure of native graphite (b).
Fig. 8 is the cycle life figure under embodiment 1 stratiform array porous carbon (a) and Comparative Examples commercialization native graphite (b) the different electric current density.
Fig. 9 be embodiment 1 stratiform array porous carbon (a) and Comparative Examples with the AC impedance figure of commercialization native graphite (b) under OCP and the equivalent circuit diagram of match (the picture left above).
Embodiment
Below in conjunction with embodiment the present invention is done further detailed description, but execution mode of the present invention is not limited thereto.
(1) 1.32g resorcinol and 2.06g formaldehyde are mixed in water, add 1.92g water, 0.00636g sodium carbonate stirred 30 minutes.
(2) polystyrene sphere that the polymerization of 2g emulsion method is prepared joins in the solution that forms in the step (1), stirs 30 minutes, filters then and obtains filter residue.
(3) filter residue that step (2) is obtained obtains stratiform array porous carbon presoma 85 ℃ of following vacuum reactions 36 hours.
(4) the stratiform array porous carbon presoma that step (3) is prepared is 300,500 ℃ of calcinings 1 hour in tube furnace under argon atmosphere, 900 ℃ of calcinings 2 hours down, and cool to room temperature under argon atmosphere obtains stratiform array porous carbon negative material.
(1) 1.32g resorcinol and 4.12g formaldehyde are mixed in water, add 2.502g water, 0.00636g sodium carbonate stirred 30 minutes.
(2) polystyrene sphere that the polymerization of 4g emulsion method is prepared joins in the solution that forms in the step (1), stirs 30 minutes, filters then and obtains filter residue.
(3) filter residue that step (2) is obtained obtains stratiform array porous carbon presoma 70 ℃ of following vacuum reactions 48 hours.
(4) the stratiform array porous carbon presoma that step (3) is prepared is 300,500 ℃ of calcinings 2 hours in tube furnace under argon atmosphere, 900 ℃ of calcinings 2 hours down, and cool to room temperature under argon atmosphere obtains stratiform array porous carbon negative material.
Embodiment 3
(1) 1.32g resorcinol and 2.505g formaldehyde are mixed in water, add 3.84g water, 0.013g sodium carbonate stirred 45 minutes.
(2) polystyrene sphere that the polymerization of 2g emulsion method is prepared joins in the solution that forms in the step (1), stirs 45 minutes, filters then and obtains filter residue.
(3) filter residue that step (2) is obtained obtains stratiform array porous carbon presoma 70 ℃ of following vacuum reactions 36 hours.
(4) the stratiform array porous carbon presoma that step (3) is prepared is 300,500 ℃ of calcinings 2 hours in tube furnace under argon atmosphere, 900 ℃ of calcinings 2 hours down, and cool to room temperature under argon atmosphere obtains stratiform array porous carbon negative material.
(1) 1.32g resorcinol and 4.824g formaldehyde are mixed in water, add 3.26g water, 0.008g sodium carbonate stirred 30 minutes.
(2) polystyrene sphere that the polymerization of 4g emulsion method is prepared joins in the solution that forms in the step (1), stirs 60 minutes, filters then and obtains filter residue.
(3) filter residue that step (2) is obtained obtains stratiform array porous carbon presoma 85 ℃ of following vacuum reactions 48 hours.
(4) the stratiform array porous carbon presoma that step (3) is prepared is 300,500 ℃ of calcinings 1 hour in tube furnace under argon atmosphere, 900 ℃ of calcinings 2 hours down, and cool to room temperature under argon atmosphere obtains stratiform array porous carbon negative material.
(1) 1.32g resorcinol and 3.56g formaldehyde are mixed in water, add 3.25g water, 0.00759g sodium carbonate stirred 30 minutes.
(2) polystyrene sphere that the polymerization of 3g emulsion method is prepared joins in the solution that forms in the step (1), stirs 30 minutes, filters then and obtains filter residue.
(3) filter residue that step (2) is obtained obtains stratiform array porous carbon presoma 85 ℃ of following vacuum reactions 72 hours.
(4) the stratiform array porous carbon presoma that step (3) is prepared is 300,500 ℃ of calcinings 1 hour in tube furnace under argon atmosphere, 900 ℃ of calcinings 3 hours down, and cool to room temperature under argon atmosphere obtains stratiform array porous carbon.
(1) 2.64g resorcinol and 4.85g formaldehyde are mixed in water, add 3.120g water, 0.00636g sodium carbonate stirred 30 minutes.
(2) polystyrene sphere that the polymerization of 2g emulsion method is prepared joins in the solution that forms in the step (1), stirs 60 minutes, filters then and obtains filter residue.
(3) filter residue that step (2) is obtained obtains stratiform array porous carbon presoma 85 ℃ of following vacuum reactions 72 hours.
(4) the stratiform array porous carbon presoma that step (3) is prepared is 300,500 ℃ of calcinings 2 hours in tube furnace under argon atmosphere, 900 ℃ of calcinings 3 hours down, and cool to room temperature under argon atmosphere obtains stratiform array porous carbon.
Embodiment 7
(1) 2.46g resorcinol and 4.82g formaldehyde are mixed in water, add 3.256g water, 0.012g sodium carbonate stirred 30 minutes.
(2) polystyrene sphere that the polymerization of 2g emulsion method is prepared joins in the solution that forms in the step (1), stirs 60 minutes, filters then and obtains filter residue.
(3) filter residue that step (2) is obtained obtains stratiform array porous carbon presoma 85 ℃ of following vacuum reactions 48 hours.
(4) the stratiform array porous carbon presoma that step (3) is prepared is 300,500 ℃ of calcinings 2 hours in tube furnace under argon atmosphere, 900 ℃ of calcinings 4 hours down, and cool to room temperature under argon atmosphere obtains stratiform array porous carbon.
The performance test experiment
Comparative Examples: business-like native graphite as negative material, is carried out chemical property and characterizes, and compare with the stratiform array porous carbon chemical property that the present invention synthesizes.
(1) Fig. 1: embodiment 1 stratiform array porous carbon is coated on the conducting resinl, carries out scanning electron microscope analysis again, test result is as shown in Figure 1.
Visible by Fig. 1, the carbon that the present invention prepares is layered porous array porous, the about 170nm of pore size, and the thickness of porous wall is greatly about 30～40nm.
(2) Fig. 2: embodiment 1 stratiform array porous carbon is carried out the X-ray diffraction test, and sweep speed is 0.1 degree per second, sweeps to 70 from 10 and spends, and its crystal formation has been carried out analytical test.
Visible by Fig. 2, the main component of the sample that the present invention prepares is a carbon, and wherein the S of trace possibly be a residual sodium peroxydisulfate in the preparation PS bead process, and Cu is the main component that is used for preparing the copper mesh of EDX sample process.
(3) Fig. 3: embodiment 1 stratiform array porous carbon is done X-ray diffraction (XRD), and test result is as shown in Figure 3.
Visible by Fig. 3, the layered porous array porous carbon that the present invention prepares is similar to the diffraction maximum of phenolic resins carbon, 22 ° and 44 ° of diffraction maximums that broad is arranged.
(4) Fig. 4: press embodiment 1 stratiform array porous carbon presoma and stratiform array porous carbon, be dispersed among the KBr, grind compressing tablet, carry out the fourier infrared test again.
Visible by Fig. 4, after the calcining, the polystyrene absworption peak has not existed, and explains that template removes.
(5) Fig. 5:, carry out the thermogravimetric test again with 100 ℃ of oven dry of embodiment 1 stratiform array porous carbon presoma elder generation 4 hours.
Visible by Fig. 5, in thermal decomposition process, presoma has 80.44% mass loss, at 400 ℃ a very big endothermic peak is arranged simultaneously, corresponding to the decomposition of polystyrene sphere.
(6) Fig. 6: stratiform array porous carbon is carried out isothermal nitrogen adsorption desorption and size distribution analysis experiment, and test result is as shown in Figure 6.
Visible by Fig. 6, stratiform array porous carbon has higher specific surface area 254m
2g
-1, total pore volume is 0.209gg
-1
(7) be work electrode with stratiform array porous carbon and native graphite respectively, the lithium sheet is to electrode, and Celgard 2400 is a barrier film, with 1mol/L LiPF
6In EC: DMC: EMC (1: 1: 1 volume ratio) is an electrolyte, is prepared into button cell.In current density from 37.2mAg
-1To 167.4mAg
-1Between carry out charge-discharge performance test, test result such as Fig. 7 and shown in Figure 8.Under OCP, frequency between the 100kHz, is an amplitude with 5mv at 10mHz, carries out ac impedance measurement, and test result is as shown in Figure 9.
Visible by Fig. 7; Compare with business-like native graphite, stratiform array porous carbon has bigger irreversible capacity first, possibly be because specific area is relatively large; In the process that forms the SEI film, lost more capacitance; Can find out under lower current density simultaneously, stratiform array porous carbon comparatively speaking, charge/discharge capacity is less.
Visible by Fig. 8, to compare with business-like native graphite, stratiform array porous carbon has higher charge/discharge capacity under high current density, possibly be because the special construction of porous carbon helps the diffusion mobility of lithium ion, makes it have high rate performance preferably.
Visible by Fig. 9, to compare with business-like native graphite, stratiform array porous carbon has less charge-transfer resistance and electrode interface resistance.Possibly be because the layer structure of stratiform array porous carbon helps the migration of lithium ion, mix with the effective of conductive agent simultaneously, effectively reduce interface resistance.
Claims (2)
1. the preparation method of a novel carbon cathode material of power lithium ion cell is characterized in that comprising the steps:
(1) sodium carbonate of the water of the formaldehyde of the resorcinol of 1.32～2.64 mass parts, 2.06～5 mass parts, 1.92～4 mass parts, 0.00636～0.013 mass parts is mixed and stirred 30～60 minutes, obtain mixed liquor;
(2) in said mixed liquor, add the polystyrene of 2～4 mass parts then, stirred 30～60 minutes, filter, obtain filter residue; Said polystyrene is the polystyrene sphere that adopts the emulsion method polymerization to prepare;
(3) said filter residue was reacted 36～72 hours under 70～85 ℃ of vacuum, obtain stratiform array porous carbon presoma;
(4) under argon atmosphere, 300～500 ℃ of calcinings in tube furnace of layered array porous carbon presoma were calcined 2～4 hours down for 1～2 hour, 900 ℃, cool to room temperature prepares carbon negative electrode material of lithium ion cell then.
2. a novel carbon cathode material of power lithium ion cell is characterized in that: adopt the said method of claim 1 to prepare.
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| CN102718205B (en) * | 2012-06-27 | 2013-11-06 | 北京科技大学 | Method for preparing three-dimensional hierarchical porous carbon |
| CN103219526A (en) * | 2013-04-02 | 2013-07-24 | 复旦大学 | Cellular morphology lithium-air battery anode with hierarchical porous structure, and preparation method thereof |
| CN109828221B (en) * | 2018-12-30 | 2022-01-21 | 武汉昊诚锂电科技股份有限公司 | Method for rapidly determining discharge capacity of lithium/manganese dioxide battery |
| CN110479211A (en) * | 2019-09-05 | 2019-11-22 | 齐鲁工业大学 | A kind of preparation method of the porous carbon materials of efficient removal dye ions |
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| WO2007137667A1 (en) * | 2006-05-31 | 2007-12-06 | Merck Patent Gmbh | Method for the production of porous carbon molds |
| CN101304085A (en) * | 2008-05-23 | 2008-11-12 | 华南师范大学 | Water-based pulping film-forming method for lithium ion battery electrode |
| CN101414674A (en) * | 2008-08-05 | 2009-04-22 | 华南师范大学 | Cathode material for lithium ion battery tin/carbon nanometer multilayer film, and preparation method and application thereof |
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| WO2007137667A1 (en) * | 2006-05-31 | 2007-12-06 | Merck Patent Gmbh | Method for the production of porous carbon molds |
| CN101304085A (en) * | 2008-05-23 | 2008-11-12 | 华南师范大学 | Water-based pulping film-forming method for lithium ion battery electrode |
| CN101414674A (en) * | 2008-08-05 | 2009-04-22 | 华南师范大学 | Cathode material for lithium ion battery tin/carbon nanometer multilayer film, and preparation method and application thereof |
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