CN103700810A - Preparation technology of negative electrode of lithium secondary battery - Google Patents
Preparation technology of negative electrode of lithium secondary battery Download PDFInfo
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- CN103700810A CN103700810A CN201310738284.XA CN201310738284A CN103700810A CN 103700810 A CN103700810 A CN 103700810A CN 201310738284 A CN201310738284 A CN 201310738284A CN 103700810 A CN103700810 A CN 103700810A
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- negative electrode
- secondary battery
- lithium secondary
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
Abstract
The invention relates to a preparation technology of a negative electrode of a lithium secondary battery. The technology comprises the steps of gluing, stirring, obtaining negative electrode pulp, rolling a conductive framework, shoving, starching, drying, rolling and cutting. According to the technology, the three-dimensional conductive framework is prepared into the lithium secondary battery charged with the negative electrode; the lithium secondary battery is low in internal resistance and excellent in electrochemical performance; the battery capacity is improved; the service life is prolonged; The negative electrode of the lithium secondary battery prepared by the technology is uniform; and the preparation technology is simple, short in flow, easy to control and high in efficiency, and is suitable for mass production.
Description
Technical field
The present invention relates to a kind of technology for preparing electrode of electrochemical secondary cell, especially a kind of negative electrode preparation technology of lithium secondary battery.
Background technology
Lithium secondary battery, since occurring, has just shown the vitality that it is powerful.Along with the particularly development of positive electrode active materials of active material, the properties of lithium battery is all greatly improved.This lithium secondary power battery tool for exploitation high-energy, environmental protection and safety and stability has very important significance, and has great market prospects and development potentiality.
At present, because the specific capacity of lithium battery has reached the limit substantially, simple its difficulty of specific capacity that improves it in positive electrode structure is very huge, because positive electrode performance give full play to the impact that can be subject to negative pole performance, therefore in order to improve the absorbent of negative pole, must in negative electrode active material, add the conductive agent of 3% left and right, electrode preparation method is all generally to adopt horizontal painting to carry out machine on Copper Foil, to be coated with one deck negative electrode active material slurry that shoe is very thin.Not only complexity is also very huge for the Tu Lvji using.Single or double is coated with to be carried out, and electrode two sides is difficult to reach very uniformity.Active slurry is coated in the just thin film forming on the metal foil material of light face, and the dilation due to active material in charge and discharge process produces the displacement between film and skeleton and easily peels, and this cycle life to battery has a great impact.Therefore the intensity that improves the loading of active material and increase electrode from technique just becomes key subjects of electrode of lithium cell preparation technology further investigation.
Foam copper is a kind of electrode skeleton material of three-dimensional conduction, is uniform-distribution with perforate that the spatial networks that are interconnected by three-dimensional in a large number form and the hole of connection in copper matrix, and porosity reaches as high as 98%.The through-hole foam copper products of Micro porosity has the performances such as good conduction that pumiceous texture and metallic copper have, heat conduction.The conductivity of foam copper and ductility are good, be widely used in the electrode skeleton material of the novel batteries such as nickel-zinc cell, double electric layer capacitor, at Ni-MH battery and nickel, on, nickel-zinc cell, also there is use, particularly foam copper is for the electrode matrix material of battery, there is comparatively significantly advantage, be therefore just subject to the attention of industry.The use on electrode of foam copper, has changed the discharge mechanism of secondary cell to a certain extent, has improved the whole system comprehensive electrochemical properties of battery.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide that a kind of technique is simple, electrode active material loading large, electrode active material good uniformity, without adding conductive agent, do not affect the negative electrode preparation technology of pole piece electric conductivity, lithium secondary battery that pole piece intensity is large.
According to technical scheme provided by the invention, the negative electrode preparation technology of described lithium secondary battery comprises the steps:
A, the deionized water of the sodium carboxymethylcellulose of 1 ~ 5 weight portion and 95 ~ 99 weight portions is put into in the slurry bucket of beater, to break into transparence colloid stand-by;
B, the negative active core-shell material of 55 ~ 65 weight portions is directly joined in transparence colloid stand-by in beater slurry bucket, stir after 3 ~ 5 hours and add the butadiene-styrene rubber breast of 1 ~ 3 weight portion to continue to stir, obtain negative electrode slurry;
C, by three-dimensional conducting matrix grain roll-in to 55% ~ 70% of original thickness;
D, the three-dimensional conducting matrix grain after roll-in is immersed in the slurry bucket of beater, the shove roller in struggling against by slurry is squeezed into negative electrode slurry in three-dimensional conducting matrix grain;
E, the three-dimensional conducting matrix grain surface of squeezing into negative electrode slurry is struck off with doctor;
F, the three-dimensional conductive paste band of squeezing into negative electrode slurry and striking off is dried through masking stove with vertical state, the temperature of masking stove is controlled at 60 ~ 90 ℃, and drying time is controlled at 0.4 ~ 1.0 hour;
G, by the three-dimensional conductive paste band roll-in of drying to 35% ~ 45% of original thickness, then through cutting the negative electrode that obtains lithium secondary battery.
Described three-dimensional conducting matrix grain is that foam copper, perforation Copper Foil or cut draw a kind of in copper mesh.
Described negative active core-shell material is a kind of or two kinds or the two or more combination in them in electrographite, native graphite, carbonaceous mesophase spherules, petroleum coke, carbon fiber, pyrolysis resin carbon, titanium dioxide.
Technique of the present invention makes with three-dimensional conducting matrix grain the lithium secondary battery that negative electrode is dressed up, and its internal resistance is low, and battery capacity increases, and extend useful life, and chemical property is good; The negative electrode of lithium secondary battery prepared by technique of the present invention is even, and manufacture craft is simple, flow process is short, easy to control, and process efficiency of the present invention is high and be suitable for large-scale production.
Accompanying drawing explanation
Fig. 1 is equipment preparation figure of the present invention.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Three-dimensional conducting matrix grain is loaded onto on unwinding device 1 and unreeled, and keep constant tension force; Enter the state of adjusting conducting matrix grain on supporting plate 3 by adjusting roller 2, to determine that it is coated with the amount of carrying out; Three-dimensional conducting matrix grain 4 enters slurry bucket 5, by 6 commutations of shove roller, and utilize shove roller 6 that slurry is got in three-dimensional conducting matrix grain 4, after the slurry that accurate doctor 7 is hung surface strikes off, enter and through upper reverse wheel 11, enter left drying tunnel 10 after preliminary oven dry of right drying tunnel 9 of masking stove 8 and dry, the electrode that then hanging is dried goes out masking stove 8 and by lower reversing roller 12, enters twin-roll machine 13 spreadings and just made anode electrode 14.
Finally according to the requirement of battery, cut out pole piece, the electrode lug of burn-oning, can stack positive pole, barrier film, negative pole successively and be wound into battery core, dress shell, the some end, welding cap cap, fluid injection, seals, just changes into and can be made into lithium secondary battery.
The present invention adopts flexible accurate scraper after hanging, electrode surface is scraped smooth, and because three-dimensional conducting matrix grain through-hole rate is high, slurry two sides is ganged up, and two sides is first drying simultaneously, and electrode two sides is more even.
Comparative example
The design parameter of the lithium secondary battery of comparative example please be provided.
A, the deionized water of the sodium carboxymethylcellulose of 1.5 weight portions and 98.5 weight portions is put into in the slurry bucket of beater, to break into transparence colloid stand-by;
B, the superconduction carbon black of the electrographite of 60 weight portions and 2 weight portions is joined respectively in the stand-by transparent colloid of beater slurry bucket, stir after 4 hours and add 2.5% butadiene-styrene rubber breast to continue to stir, obtain negative electrode slurry;
C, be coated with shoe machine by the cathode size making be coated with carry out in the one side of Copper Foil dry, rolling, then upset is coated with anode sizing agent another side, the oven dry of carrying out at Copper Foil;
D, the two rollers of use are rolled into 110 ~ 130 micron thickness by the pole piece of oven dry;
E, by pole piece after spreading through cutting the negative electrode that obtains lithium secondary battery;
F, then itself and barrier film, positive pole are stacked successively and be wound into battery core, dress shell, the some end, welding cap cap, fluid injection, seal, change into and make lithium secondary battery.
After tested, average internal resistance 33 milliohms of the lithium secondary battery of 18650 models made from this technique, average size is in 1980 MAH left and right.
Embodiment 1
A kind of negative electrode preparation technology of lithium secondary battery comprises the steps:
A, the deionized water of the sodium carboxymethylcellulose of 1 weight portion and 95 weight portions is put into in the slurry bucket of beater, to break into transparence colloid stand-by;
B, the electrographite of 55 weight portions is directly joined in transparence colloid stand-by in beater slurry bucket, stir after 4 hours and add the butadiene-styrene rubber breast of 1 weight portion to continue to stir, obtain negative electrode slurry;
C, by foam copper roll-in to 55 ~ 70% of original thickness;
D, foam copper after roll-in is immersed in the slurry bucket of beater, the shove roller in struggling against by slurry is got into negative slurry in foam copper;
E, the foam copper surface of getting into cathode size is struck off with doctor;
F, the three-dimensional conductive paste band of squeezing into cathode size and striking off is dried through masking stove with vertical state, the temperature of masking stove is controlled at 60 ~ 90 ℃, and drying time is controlled at 0.4 ~ 1.0 hour;
G, by the three-dimensional conductive paste band roll-in of drying to 35% ~ 45% of original thickness, then through cutting the negative electrode that obtains lithium secondary battery.
The negative electrode that the negative electrode alternative costs embodiment of comparative example is made to be assembled into model be after 18650 lithium secondary battery, after tested, the internal resistance of lithium secondary battery is 24.5 milliohms, the ratio of comparing has reduced by 8.5 milliohms, the capacity of lithium secondary battery is increased to 2172.06 MAHs, and the ratio of comparing has improved 9.7%.
Embodiment 2
A negative electrode preparation technology for lithium secondary battery, is characterized in that this preparation technology comprises the steps:
A, the deionized water of the sodium carboxymethylcellulose of 5 weight portions and 99 weight portions is put into in the slurry bucket of beater, to break into transparence colloid stand-by;
B, the native graphite of 65 weight portions is directly joined in transparence colloid stand-by in beater slurry bucket, stir after 4 hours and add the butadiene-styrene rubber breast of 3 weight portions to continue to stir, obtain negative electrode slurry;
C, by cutting, draw wire roll to be depressed into 80% ~ 95% of original thickness;
D, micro-after roll-in cut in the slurry bucket that draws copper mesh to immerse beater, the shove roller in struggling against by slurry micro-cut to draw in copper mesh, get into negative slurry;
E, draw copper mesh surface to strike off with doctor micro-the cutting of getting into cathode size;
F, the three-dimensional conductive paste band of squeezing into cathode size and striking off is dried through masking stove with vertical state, the temperature of masking stove is controlled at 60 ~ 90 ℃, and drying time is controlled at 0.4 ~ 1.0 hour;
G, by the three-dimensional conductive paste band roll-in of drying to 35% ~ 45% of original thickness, then through cutting the negative electrode that obtains lithium secondary battery.
The negative electrode that the negative electrode alternative costs embodiment of comparative example is made to be assembled into model be after 18650 lithium secondary battery, after tested, the internal resistance of lithium secondary battery is 25 milliohms, the ratio of comparing has reduced by 8 milliohms, the capacity of lithium secondary battery is increased to 2178 MAHs, and the ratio of comparing has improved 10%.
Embodiment 3
A kind of negative electrode preparation technology of lithium secondary battery comprises the steps:
A, the deionized water of the sodium carboxymethylcellulose of 3 weight portions and 97 weight portions is put into in the slurry bucket of beater, to break into transparence colloid stand-by;
B, the petroleum coke of 60 weight portions is directly joined in transparence colloid stand-by in beater slurry bucket, stir after 4 hours and add the butadiene-styrene rubber breast of 2 weight portions to continue to stir, obtain negative electrode slurry;
C, the Copper Foil of boring a hole are adjusted smooth by adjusting roller;
D, the micropunch Copper Foil after adjusting is immersed in the slurry bucket of beater, the shove roller in struggling against by slurry is got into negative slurry on micropunch Copper Foil;
E, the micropunch copper foil surface of getting into cathode size is struck off with doctor;
F, the three-dimensional conductive paste band of squeezing into cathode size and striking off is dried through masking stove with vertical state, the temperature of masking stove is controlled at 60 ~ 90 ℃, and drying time is controlled at 0.4 ~ 1.0 hour;
G, by the three-dimensional conductive paste band roll-in of drying to 35% ~ 45% of original thickness, then through cutting the negative electrode that obtains lithium secondary battery.
The negative electrode that the negative electrode alternative costs embodiment of comparative example is made to be assembled into model be after 18650 lithium secondary battery, after tested, the internal resistance of lithium secondary battery is 25.9 milliohms, the ratio of comparing has reduced by 7.1 milliohms, the capacity of lithium secondary battery is 2187.9 MAHs, and the ratio of comparing has improved 10.5%.
Claims (3)
1. a negative electrode preparation technology for lithium secondary battery, is characterized in that this preparation technology comprises the steps:
A, the deionized water of the sodium carboxymethylcellulose of 1 ~ 5 weight portion and 95 ~ 99 weight portions is put into in the slurry bucket of beater, to break into transparence colloid stand-by;
B, the negative active core-shell material of 55 ~ 65 weight portions is directly joined in transparence colloid stand-by in beater slurry bucket, stir after 3 ~ 5 hours and add the butadiene-styrene rubber breast of 1 ~ 3 weight portion to continue to stir, obtain negative electrode slurry;
C, by three-dimensional conducting matrix grain roll-in to 55% ~ 70% of original thickness;
D, the three-dimensional conducting matrix grain after roll-in is immersed in the slurry bucket of beater, the shove roller in struggling against by slurry is squeezed into negative electrode slurry in three-dimensional conducting matrix grain;
E, the three-dimensional conducting matrix grain surface of squeezing into negative electrode slurry is struck off with doctor;
F, the three-dimensional conductive paste band of squeezing into negative electrode slurry and striking off is dried through masking stove with vertical state, the temperature of masking stove is controlled at 60 ~ 90 ℃, and drying time is controlled at 0.4 ~ 1.0 hour;
G, by the three-dimensional conductive paste band roll-in of drying to 35% ~ 45% of original thickness, then through cutting the negative electrode that obtains lithium secondary battery.
2. the negative electrode preparation technology of lithium secondary battery as claimed in claim 1, is characterized in that: described three-dimensional conducting matrix grain is that foam copper, perforation Copper Foil or cut draws a kind of in copper mesh.
3. the negative electrode preparation technology of lithium secondary battery as claimed in claim 1, is characterized in that: described negative active core-shell material is a kind of or their two kinds or the two or more combinations in electrographite, native graphite, carbonaceous mesophase spherules, petroleum coke, carbon fiber, pyrolysis resin carbon, titanium dioxide.
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| CN201310738284.XA CN103700810A (en) | 2013-12-27 | 2013-12-27 | Preparation technology of negative electrode of lithium secondary battery |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109641404A (en) * | 2016-08-24 | 2019-04-16 | 巴斯夫欧洲公司 | Device and method for impregnating fibrous structures |
| CN112357959A (en) * | 2020-10-19 | 2021-02-12 | 成都先进金属材料产业技术研究院有限公司 | Preparation method of nano vanadium dioxide/reticular graphite-based composite electrode material |
| CN114054822A (en) * | 2021-12-21 | 2022-02-18 | 湖南科技大学 | Self-adaptive milling composite cutter |
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| CN101692491A (en) * | 2009-09-22 | 2010-04-07 | 哈尔滨工业大学 | Preparation method of three-dimensional foamed cobalt oxide cathode |
| CN102683655A (en) * | 2012-04-26 | 2012-09-19 | 上海杉杉科技有限公司 | Three-dimensional porous silicon-based composite negative electrode material of lithium ion cell and preparation method thereof |
| CN103367754A (en) * | 2013-07-29 | 2013-10-23 | 河南环宇赛尔新能源科技有限公司 | Soft-package aqueous lithium iron phosphate power battery and making method thereof |
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2013
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Patent Citations (4)
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| US20030039890A1 (en) * | 2000-02-22 | 2003-02-27 | Kyung-Suk Yun | Carbon electrode coated with porous metal film, its fabrication method and lithium secondary battery using the same |
| CN101692491A (en) * | 2009-09-22 | 2010-04-07 | 哈尔滨工业大学 | Preparation method of three-dimensional foamed cobalt oxide cathode |
| CN102683655A (en) * | 2012-04-26 | 2012-09-19 | 上海杉杉科技有限公司 | Three-dimensional porous silicon-based composite negative electrode material of lithium ion cell and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109641404A (en) * | 2016-08-24 | 2019-04-16 | 巴斯夫欧洲公司 | Device and method for impregnating fibrous structures |
| CN109641404B (en) * | 2016-08-24 | 2021-08-17 | 巴斯夫欧洲公司 | Device and method for impregnating a fibrous structure |
| US11565442B2 (en) | 2016-08-24 | 2023-01-31 | Basf Se | Device and method for impregnating fiber structures |
| CN112357959A (en) * | 2020-10-19 | 2021-02-12 | 成都先进金属材料产业技术研究院有限公司 | Preparation method of nano vanadium dioxide/reticular graphite-based composite electrode material |
| CN112357959B (en) * | 2020-10-19 | 2022-07-29 | 成都先进金属材料产业技术研究院股份有限公司 | Preparation method of nano vanadium dioxide/reticular graphite-based composite electrode material |
| CN114054822A (en) * | 2021-12-21 | 2022-02-18 | 湖南科技大学 | Self-adaptive milling composite cutter |
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