CN102610825B - Manufacturing method of cathode electrode plate for lithium battery - Google Patents

Manufacturing method of cathode electrode plate for lithium battery Download PDF

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CN102610825B
CN102610825B CN201210081958.9A CN201210081958A CN102610825B CN 102610825 B CN102610825 B CN 102610825B CN 201210081958 A CN201210081958 A CN 201210081958A CN 102610825 B CN102610825 B CN 102610825B
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lithium battery
electrode plate
cathode electrode
carbon black
manufacture method
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CN102610825A (en
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王皎月
邓孝天
刘顺明
张琦
汪洋
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Dazhou Iron and Steel Group Co Ltd
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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
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a manufacturing method of a cathode electrode plate for a lithium battery, comprising the following steps: evenly mixing active graphite, LiV3O8, activated carbon black powder and binder according to certain mass ratio to form a mixture; pressing the mixture and a copper mesh at 330-350 degrees centigrade under a condition of pressure of 20-30 Mpa to form an electrode plate for the lithium battery, then drying at 80-120 degrees centigrade in vacuum; putting the dried electrode plate into concentrated sulfuric acid, processing for 8-12 h, cleaning with deionized water, drying, then putting into a muffle furnace, and drying at 180-240 degrees centigrade for 4-6 h to manufacture the cathode electrode plate for the lithium battery. Compared with the prior art, in the manufacturing method of the cathode electrode plate for the lithium battery, the graphitized carbon black and LiV3O8 is added into the active graphite to produce cathode materials for the lithium battery, therefore, specific surface area of a graphite electrode is increased to increase path of current transmission, enhance conductively of the electrode, prolong service life and adapt to electrolyte.

Description

A kind of manufacture method of cathode electrode plate for lithium battery
Technical field
The present invention relates to field of battery production, exactly refer to a kind of manufacture method of cathode electrode plate for lithium battery.
Background technology
The energy and environment are two Tough questions that the mankind stride into faced by 21 century, and tapping a new source of energy with renewable and clean energy resource is one of material technical field of World Economics most.Lithium ion battery due to its have that operating voltage is high, quality is light, specific energy is large, self discharge is little, have extended cycle life, the outstanding advantages such as memory-less effect, non-environmental-pollution, becoming the ideal source of various fields, is also the first-selected power supply of following electric automobile high-energy power battery.
Negative el, as the important component part of lithium battery, has extremely important effect.What current utilization was more is native graphite, the structural integrity of graphite, and embedding lithium position is many, so capacity is high, be ideal lithium battery negative material, but it still have obvious shortcoming, as: the shortcomings such as more responsive to electrolyte, heavy-current discharge performance is poor, cycle life difference.
Summary of the invention
For above-mentioned defect, the technical problem that the present invention solves is the manufacture method providing a kind of cathode electrode plate for lithium battery, the carbon black add graphitization in activation graphite after and LiV 3o 8produce lithium battery negative material, to reach the specific area of increase graphite electrode to increase the path of current delivery, conductivity, the cycle life of intensifier electrode and to adapt to the performances such as electrolyte.
In order to solve above technical problem, the manufacture method of cathode electrode plate for lithium battery provided by the invention, comprises the following steps:
(1) by Activated Graphite, LiV 3o 8, activated carbon black powder, binding agent mix according to following mass ratio, forms mixture:
(2) under 330 DEG C of-350 DEG C of conditions, mixture and copper mesh are pressed into lithium battery battery lead plate with the pressure of 20MPa-30MPa, then dry under the vacuum condition of 80 DEG C-120 DEG C;
(3) battery lead plate of oven dry is put process 8h-12h in concentrated sulfuric acid, after cleaning dry with deionized water, then be put in Muffle furnace, toast 4-6h at temperature is 180 DEG C-240 DEG C after, make cathode electrode plate for lithium battery.
Preferably, in step (1), the preparation process of activated carbon black powder is as follows:
(S1) hard (carbon) black is placed in the environment being full of argon shield gas, graphitization after constant temperature 60min 70min under 2500 DEG C of-3000 DEG C of high temperature;
(S2) graphited carbon black is worn into the powdery of below 120 orders;
(S3) carbon powder is heated to 800-950 DEG C in nitrogen, stirs gradually and add H 2o 2, then keep 2-3 hour at 75-95 DEG C, room temperature cools;
(S4) carbon powder 80-120 DEG C of oven dry under vacuum.
Preferably, in step (S1), during intensification: room temperature-1300 DEG C of sections heat up according to 350-400 DEG C/h; 1300-2000 DEG C of section heats up according to 100-150 DEG C/h; 2000 DEG C-highest temperature section heats up according to 400-500 DEG C/h, is then incubated 0.8-1.5 hour.
4, the manufacture method of cathode electrode plate for lithium battery according to claim 2, is characterized in that, in step (S2), graphited carbon black is worn into the powdery of below 100 orders.
Preferably, in step (1), LiV 3o 8preparation process as follows:
(P1) by NH 4vO 3carry out " quenching " process, obtain V 2o 5colloidal sol;
(P2) by V 2o 5colloidal sol stoichiometrically 1.5-2.5: 1 mixes with LiOH solution;
(P3), under the high temperature then more than 650-1000 DEG C, after frit reaction 8-12 hour, the alloy liquid of melting is dropped in frozen water rapidly and cools rapidly, drying at room temperature;
(P4) heat-treat at the temperature of 180-280 DEG C, be ground to the powdery of below 200 orders.
Preferably, in step (1) by Activated Graphite, LiV 3o 8, activated carbon black powder, binding agent mixed by electromagnetic stirrer.
Preferably, in step (2), described binding agent is PVdF/N-methyl pyrrolidone, mixture is heated to 330-340 DEG C, after to be bonded dose of thawing, by the pressure pressure of 14MPa-18MPa, mixture and copper mesh are pressed into lithium battery battery lead plate, in vacuum condition 100 DEG C oven dry.
Preferably, in step (3), the mass fraction of the concentrated sulfuric acid is 70%-98%.
Preferably, in step (3), the battery lead plate of oven dry is put after processing 10h in concentrated sulfuric acid and clean with deionized water.
Preferably, in step (3), lithium battery anode battery lead plate is put in Muffle furnace after need drying again and activates, toast 4-5h at temperature is 220 DEG C after.
The manufacture method of cathode electrode plate for lithium battery provided by the invention, by Activated Graphite, LiV 3o 8, activated carbon black powder, binding agent mix formation mixture according to certain mass ratio; Under 330 DEG C of-350 DEG C of conditions, mixture and copper mesh are pressed into lithium battery battery lead plate with the pressure of 20MPa-30MPa, then dry under the vacuum condition of 80 DEG C-120 DEG C; The battery lead plate of oven dry is put and processes 8h-12h in concentrated sulfuric acid, after cleaning oven dry with deionized water, then be put in Muffle furnace, toast 4-6h at temperature is 180 DEG C-240 DEG C after, make cathode electrode plate for lithium battery.Compared with prior art, the manufacture method of cathode electrode plate for lithium battery provided by the invention, the carbon black add graphitization in activation graphite after and LiV 3o 8produce lithium battery negative material, to reach the specific area of increase graphite electrode to increase the path of current delivery, conductivity, the cycle life of intensifier electrode and to adapt to the performances such as electrolyte.
Accompanying drawing explanation
The process chart of the manufacture method of the cathode electrode plate for lithium battery that Fig. 1 provides for the embodiment of the present invention.
Embodiment
In order to those skilled in the art can understand technical scheme provided by the present invention better, set forth below in conjunction with specific embodiment.
Refer to Fig. 1, this figure is the process chart of the manufacture method of cathode electrode plate for lithium battery provided by the invention.
Embodiment 1
The manufacture method of the cathode electrode plate for lithium battery that the present embodiment provides, comprises the following steps:
(1) by Activated Graphite, LiV 3o 8, activated carbon black powder, binding agent mixed by electromagnetic stirrer according to following mass ratio, form mixture, wherein binding agent is PVdF/N-methyl pyrrolidone:
(2) use the pressure of 20MPa under 330 DEG C of conditions, after to be bonded dose of thawing, mixture and copper mesh are pressed into lithium battery battery lead plate, fine and close vanadium battery electrode plate can be obtained, prevent leakage, then dry under the vacuum condition of 80 DEG C, anti-oxidation, prevent the generation of crackle;
(3) battery lead plate of oven dry being placed on mass fraction is clean with deionized water after processing 8h in the concentrated sulfuric acid of 70%, and it is carry out chemical treatment to electrode plate surface that pole plate puts process in concentrated sulfuric acid, can improve its electro-chemical activity; The negative el of lithium battery need be dried and is put in Muffle furnace more afterwards, just makes after toasting 4 at temperature is 180 DEG C.
In addition in step (1), the preparation process of activated carbon black powder is as follows:
(S1) hard (carbon) black is placed in the environment being full of argon shield gas, graphitization after constant temperature 60min-70min under 2500 DEG C of-3000 DEG C of high temperature, during intensification: room temperature-1300 DEG C of sections heat up according to 350-400 DEG C/h; 1300-2000 DEG C of section heats up according to 100-150 DEG C/h; 2000 DEG C-highest temperature section heats up according to 400-500 DEG C/h, is then incubated 0.8 hour;
(S2) graphited carbon black is worn into the powdery of below 120 orders;
(S3) carbon powder is heated to 800 DEG C in nitrogen, stir gradually and add hydrogen peroxide, then keep 2 hours at 75 DEG C, room temperature cools; Carbon black belongs to the carbon materials of oleophylic, adopt aqueous binders prepare battery material, carbon black is dispersed very poor in the slurry, with hydrogen peroxide carbon black is oxidized, activation processing, the specific area of carbon black can be increased, reduce resistance, improve the hydrophily of carbon black, conductivity and cycle characteristics;
(S4) carbon powder 80 DEG C of oven dry under vacuum.
So-called graphitization baked article is placed in protective medium in graphitizing furnace be heated to high temperature; so-called graphitization, makes hexagonal carbon atomic plane network become from the unordered overlap of two-dimensional space the high-temperature hot heat treatment process that three-dimensional ordered overlaid has graphite-structure exactly.Be exactly carbon black by high temperature process, thus increase conductivity, reduce the resistivity of carbon black.
Further, in step (1), LiV 3o 8preparation process as follows:
(P1) by NH 4vO 3carry out " quenching " process, obtain V 2o 5colloidal sol;
(P2) by V 2o 5colloidal sol stoichiometrically mixes with LiOH solution at 1.5: 1;
(P3), under the high temperature then more than 650 DEG C, the alloy liquid of melting, after 8 hours, drops in frozen water rapidly and cools rapidly, drying at room temperature by frit reaction; Under high temperature, lithium is different from the volatilization degree of vanadium and the corrosion equal loss degree of barium oxide to vessel is different, and make the ratio of lithium and vanadium be difficult to control, the product obtained also evenly differs, and degree of crystallinity is high, and its structure is unfavorable for playing LiV 3o 8high capacity characteristics, specific capacity is low, and cycle characteristics is poor, and the technological means that available high temperature cools fast is improved conventional high-temperature solid phase method, Be very effective; Residual fraction hydrone in product, these hydrones and LiV 3o 8in conjunction with very tight, residual hydrone both increased LiV 3o 8interlamellar spacing, in turn increase the diffusion admittance of Li+, be conducive to the embedding of Li+;
(P4) heat-treat at the temperature of 180-280 DEG C, be ground to the powdery of below 200 orders.
Graphited carbon black is worn into below 120 orders, LiV 3o 8the powdery being milled to below 200 orders fully mixes to allow, and increases the interlamellar spacing of electrode, be beneficial to the embedding of Li+.
Embodiment 2
The manufacture method of the cathode electrode plate for lithium battery that the present embodiment provides, comprises the following steps:
(1) by Activated Graphite, LiV 3o 8, activated carbon black powder, binding agent mixed by electromagnetic stirrer according to following mass ratio, form mixture, wherein binding agent is PVdF/N-methyl pyrrolidone:
(2) use the pressure of 30MPa under 350 DEG C of conditions, after to be bonded dose of thawing, mixture and copper mesh are pressed into lithium battery battery lead plate, fine and close vanadium battery electrode plate can be obtained, prevent leakage, then dry under the vacuum condition of 120 DEG C, anti-oxidation, prevent the generation of crackle;
(3) battery lead plate of oven dry being placed on mass fraction is clean with deionized water after processing 12h in the concentrated sulfuric acid of 98%, and it is carry out chemical treatment to electrode plate surface that pole plate puts process in concentrated sulfuric acid, can improve its electro-chemical activity; The negative el of lithium battery need be dried and is put in Muffle furnace more afterwards, just makes after toasting 6h at temperature is 240 DEG C.
In addition in step (1), the preparation process of activated carbon black powder is as follows:
(S1) hard (carbon) black is placed in the environment being full of argon shield gas, graphitization after constant temperature 60min-70min under 2500 DEG C of-3000 DEG C of high temperature, during intensification: room temperature-1300 DEG C of sections heat up according to 350-400 DEG C/h; 1300-2000 DEG C of section heats up according to 100-150 DEG C/h; 2000 DEG C-highest temperature section heats up according to 400-500 DEG C/h, is then incubated 1.5 hours;
(S2) graphited carbon black is worn into the powdery of below 100 orders;
(S3) carbon powder is heated to 950 DEG C in nitrogen, stir gradually and add hydrogen peroxide, then keep 3 hours at 95 DEG C, room temperature cools; Carbon black belongs to the carbon materials of oleophylic, adopt aqueous binders prepare battery material, carbon black is dispersed very poor in the slurry, with hydrogen peroxide carbon black is oxidized, activation processing, the specific area of carbon black can be increased, reduce resistance, improve the hydrophily of carbon black, conductivity and cycle characteristics;
(S4) carbon powder 120 DEG C of oven dry under vacuum.
So-called graphitization baked article is placed in protective medium in graphitizing furnace be heated to high temperature; so-called graphitization, makes hexagonal carbon atomic plane network become from the unordered overlap of two-dimensional space the high-temperature hot heat treatment process that three-dimensional ordered overlaid has graphite-structure exactly.Be exactly carbon black by high temperature process, thus increase conductivity, reduce the resistivity of carbon black.
Further, in step (1), LiV 3o 8preparation process as follows:
(P1) by NH 4vO 3carry out " quenching " process, obtain V 2o 5colloidal sol;
(P2) by V 2o 5colloidal sol stoichiometrically mixes with LiOH solution at 2.5: 1;
(P3), under the high temperature then more than 1000 DEG C, the alloy liquid of melting, after 12 hours, drops in frozen water rapidly and cools rapidly, drying at room temperature by frit reaction; Under high temperature, lithium is different from the volatilization degree of vanadium and the corrosion equal loss degree of barium oxide to vessel is different, and make the ratio of lithium and vanadium be difficult to control, the product obtained also evenly differs, and degree of crystallinity is high, and its structure is unfavorable for playing LiV 3o 8high capacity characteristics, specific capacity is low, and cycle characteristics is poor, and the technological means that available high temperature cools fast is improved conventional high-temperature solid phase method, Be very effective; Residual fraction hydrone in product, these hydrones and LiV 3o 8in conjunction with very tight, residual hydrone both increased LiV 3o 8interlamellar spacing, in turn increase the diffusion admittance of Li+, be conducive to the embedding of Li+;
(P4) heat-treat at the temperature of 180-280 DEG C, be ground to the powdery of below 200 orders.
Graphited carbon black is worn into below 100 orders, LiV 3o 8the powdery being milled to below 200 orders fully mixes to allow, and increases the interlamellar spacing of electrode, be beneficial to the embedding of Li+.
Embodiment 3
The manufacture method of the cathode electrode plate for lithium battery that the present embodiment provides, comprises the following steps:
(1) by Activated Graphite, LiV 3o 8, activated carbon black powder, binding agent mixed by electromagnetic stirrer according to following mass ratio, form mixture, wherein binding agent is PVdF/N-methyl pyrrolidone:
(2) use the pressure of 25MPa under 340 DEG C of conditions, after to be bonded dose of thawing, mixture and copper mesh are pressed into lithium battery battery lead plate, fine and close vanadium battery electrode plate can be obtained, prevent leakage, then dry under the vacuum condition of 100 DEG C, anti-oxidation, prevent the generation of crackle;
(3) battery lead plate of oven dry being placed on mass fraction is clean with deionized water after processing 10h in the concentrated sulfuric acid of 90%, and it is carry out chemical treatment to electrode plate surface that pole plate puts process in concentrated sulfuric acid, can improve its electro-chemical activity; The negative el of lithium battery need be dried and is put in Muffle furnace more afterwards, just makes after toasting 5h at temperature is 220 DEG C.
In addition in step (1), the preparation process of activated carbon black powder is as follows:
(S1) hard (carbon) black is placed in the environment being full of argon shield gas, graphitization after constant temperature 65min under 2800 DEG C of high temperature, during intensification: room temperature-1300 DEG C of sections heat up according to 350-400 DEG C/h; 1300-2000 DEG C of section heats up according to 100-150 DEG C/h; 2000 DEG C-highest temperature section heats up according to 400-500 DEG C/h, is then incubated 0.8-1.5 hour;
(S2) graphited carbon black is worn into the powdery of below 80 orders;
(S3) carbon powder is heated to 900 DEG C in nitrogen, stir gradually and add hydrogen peroxide, then keep 2.5 hours at 85 DEG C, room temperature cools; Carbon black belongs to the carbon materials of oleophylic, adopt aqueous binders prepare battery material, carbon black is dispersed very poor in the slurry, with hydrogen peroxide carbon black is oxidized, activation processing, the specific area of carbon black can be increased, reduce resistance, improve the hydrophily of carbon black, conductivity and cycle characteristics;
(S4) carbon powder 100 DEG C of oven dry under vacuum.
So-called graphitization baked article is placed in protective medium in graphitizing furnace be heated to high temperature; so-called graphitization, makes hexagonal carbon atomic plane network become from the unordered overlap of two-dimensional space the high-temperature hot heat treatment process that three-dimensional ordered overlaid has graphite-structure exactly.Be exactly carbon black by high temperature process, thus increase conductivity, reduce the resistivity of carbon black.
Further, in step (1), LiV 3o 8preparation process as follows:
(P1) by NH 4vO 3carry out " quenching " process, obtain V 2o 5colloidal sol;
(P2) by V 2o 5colloidal sol stoichiometrically mixes with LiOH solution at 2: 1;
(P3), under the high temperature then more than 800 DEG C, the alloy liquid of melting, after 10 hours, drops in frozen water rapidly and cools rapidly, drying at room temperature by frit reaction; Under high temperature, lithium is different from the volatilization degree of vanadium and the corrosion equal loss degree of barium oxide to vessel is different, and make the ratio of lithium and vanadium be difficult to control, the product obtained also evenly differs, and degree of crystallinity is high, and its structure is unfavorable for playing LiV 3o 8high capacity characteristics, specific capacity is low, and cycle characteristics is poor, and the technological means that available high temperature cools fast is improved conventional high-temperature solid phase method, Be very effective; Residual fraction hydrone in product, these hydrones and LiV 3o 8in conjunction with very tight, residual hydrone both increased LiV 3o 8interlamellar spacing, in turn increase the diffusion admittance of Li+, be conducive to the embedding of Li+;
(P4) heat-treat at the temperature of 180-280 DEG C, be ground to the powdery of below 200 orders.
Graphited carbon black is worn into below 120 orders, LiV 3o 8the powdery being milled to below 200 orders fully mixes to allow, and increases the interlamellar spacing of electrode, be beneficial to the embedding of Li+.
Compared with prior art, the manufacture method of cathode electrode plate for lithium battery provided by the invention, the carbon black add graphitization in activation graphite after and LiV 3o 8produce lithium battery negative material, to reach the specific area of increase graphite electrode to increase the path of current delivery, conductivity, the cycle life of intensifier electrode and to adapt to the performances such as electrolyte.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.

Claims (8)

1. a manufacture method for cathode electrode plate for lithium battery, is characterized in that, comprises the following steps:
(1) by Activated Graphite, LiV 3o 8, activated carbon black powder, binding agent mix according to following mass ratio, forms mixture:
The preparation process of activated carbon black powder is as follows:
(S1) hard (carbon) black is placed in the environment being full of argon shield gas, graphitization after constant temperature 60min ~ 70min under 2500 DEG C ~ 3000 DEG C high temperature;
(S2) graphited carbon black is worn into the powdery of below 120 orders;
(S3) carbon powder is heated to 800 ~ 950 DEG C in nitrogen, stirs gradually and add H 2o 2, then keep 2 ~ 3 hours at 75 ~ 95 DEG C, room temperature cools;
(S4) carbon powder 80 ~ 120 DEG C of oven dry under vacuum;
(2) under 330 DEG C ~ 350 DEG C conditions, mixture and copper mesh are pressed into lithium battery battery lead plate with the pressure of 20MPa ~ 30MPa, then dry under the vacuum condition of 80 DEG C ~ 120 DEG C;
(3) battery lead plate of oven dry is put process 8h ~ 12h in concentrated sulfuric acid, after cleaning dry with deionized water, then be put in Muffle furnace, toast 4 ~ 6h at temperature is 180 DEG C ~ 240 DEG C after, make cathode electrode plate for lithium battery.
2. the manufacture method of cathode electrode plate for lithium battery according to claim 1, is characterized in that, in step (S1), during intensification: room temperature ~ 1300 DEG C section heats up according to 350 ~ 400 DEG C/h; 1300 ~ 2000 DEG C of sections heat up according to 100 ~ 150 DEG C/h; 2000 DEG C ~ highest temperature section heats up according to 400 ~ 500 DEG C/h, is then incubated 60min ~ 70min.
3. the manufacture method of cathode electrode plate for lithium battery according to claim 1, is characterized in that, in step (1), and LiV 3o 8preparation process as follows:
(P1) by NH 4vO 3carry out " quenching " process, obtain V 2o 5colloidal sol;
(P2) by V 2o 5colloidal sol and LiOH solution stoichiometrically 1.5-2.5:1 mix;
(P3) then under the high temperature of 650-1000 DEG C, the alloy liquid of melting, after 8-12 hour, drops in frozen water rapidly and cools rapidly, drying at room temperature by frit reaction;
(P4) heat-treat at the temperature of 180-280 DEG C, be ground to the powdery of below 200 orders.
4. the manufacture method of cathode electrode plate for lithium battery according to claim 1, is characterized in that, by Activated Graphite, LiV in step (1) 3o 8, activated carbon black powder, binding agent mixed by electromagnetic stirrer.
5. the manufacture method of cathode electrode plate for lithium battery according to claim 1, it is characterized in that, in step (2), described binding agent is PVdF/N-methyl pyrrolidone, mixture is heated to 330 ~ 340 DEG C, after to be bonded dose of thawing, with the pressure of 20MPa ~ 30MPa, mixture and copper mesh are pressed into lithium battery battery lead plate, in vacuum condition 100 DEG C oven dry.
6. the manufacture method of cathode electrode plate for lithium battery according to claim 1, is characterized in that, in step (3), the mass fraction of the concentrated sulfuric acid is 70% ~ 98%.
7. the manufacture method of cathode electrode plate for lithium battery according to claim 1, is characterized in that, is put by the battery lead plate of oven dry after processing 10h in concentrated sulfuric acid and clean with deionized water in step (3).
8. the manufacture method of cathode electrode plate for lithium battery according to claim 1, it is characterized in that, in step (3), the battery lead plate of oven dry is put and process 10h in concentrated sulfuric acid, after cleaning oven dry with deionized water, be put into again in Muffle furnace, toast 4 ~ 5h at temperature is 220 DEG C after, make cathode electrode plate for lithium battery.
CN201210081958.9A 2012-03-26 2012-03-26 Manufacturing method of cathode electrode plate for lithium battery Active CN102610825B (en)

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CN103606680B (en) * 2013-12-05 2015-10-21 百吉瑞（天津）新能源有限公司 The preparation method of the nitrogenous carbon fibre web negative material of a kind of native graphite compound
CN104043808B (en) * 2014-06-20 2016-04-13 北京科技大学 One adds copper mesh compound high silicon iron-base alloy battery lead plate and manufacture method thereof
CN110964349B (en) * 2018-09-30 2021-08-17 山东欧铂新材料有限公司 Oxidation modified carbon black and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5039582A (en) * 1989-04-12 1991-08-13 Consiglio Nazionale Delle Ricerche High energy and high power lithium storage batteries, and method for producing the same
CN101221853A (en) * 2007-12-13 2008-07-16 复旦大学 Semi-solid state or full-solid state water system super capacitor
CN101656329A (en) * 2009-09-22 2010-02-24 西安交通大学 Preparation method of inorganic aqueous solution lithium ion battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5039582A (en) * 1989-04-12 1991-08-13 Consiglio Nazionale Delle Ricerche High energy and high power lithium storage batteries, and method for producing the same
CN101221853A (en) * 2007-12-13 2008-07-16 复旦大学 Semi-solid state or full-solid state water system super capacitor
CN101656329A (en) * 2009-09-22 2010-02-24 西安交通大学 Preparation method of inorganic aqueous solution lithium ion battery

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