CN108217640B - Preparation method of negative electrode of lithium ion battery capable of being used for quick charging - Google Patents
Preparation method of negative electrode of lithium ion battery capable of being used for quick charging Download PDFInfo
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- CN108217640B CN108217640B CN201810017551.7A CN201810017551A CN108217640B CN 108217640 B CN108217640 B CN 108217640B CN 201810017551 A CN201810017551 A CN 201810017551A CN 108217640 B CN108217640 B CN 108217640B
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 28
- 239000010439 graphite Substances 0.000 claims abstract description 28
- 239000007770 graphite material Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 18
- 230000001590 oxidative effect Effects 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 10
- 150000002500 ions Chemical class 0.000 claims abstract description 10
- 239000011229 interlayer Substances 0.000 claims abstract description 9
- 238000009830 intercalation Methods 0.000 claims abstract description 8
- 230000002687 intercalation Effects 0.000 claims abstract description 7
- 230000002378 acidificating effect Effects 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 14
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000004323 potassium nitrate Substances 0.000 claims description 6
- 235000010333 potassium nitrate Nutrition 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 239000010410 layer Substances 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 150000001340 alkali metals Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 6
- 230000005012 migration Effects 0.000 abstract description 6
- 238000013508 migration Methods 0.000 abstract description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052744 lithium Inorganic materials 0.000 abstract description 5
- 239000007773 negative electrode material Substances 0.000 abstract description 5
- 210000001787 dendrite Anatomy 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 239000010406 cathode material Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 11
- 238000003756 stirring Methods 0.000 description 8
- 239000003518 caustics Substances 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000033764 rhythmic process Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a method for modifying a graphite cathode of a quick-charging lithium ion battery, belonging to the field of quick charging of lithium ion batteries. The invention treats the layered graphite by a method of intercalation of interlayer ions under acid corrosion and oxidizing conditions, and is used for the negative electrode material of the quick-charging lithium ion battery. The technical scheme is that the layered graphite is placed in an acidic mixed solution with a certain concentration and a certain oxidability, the temperature is controlled to be about 25-35 ℃, and the layered graphite is filtered and washed after being mixed for a certain time. The graphite material which is porous and has larger interlayer spacing is obtained by the corrosion of oxidizing acid and the action of embeddable ions and is used for the negative electrode of the quick-charging lithium ion battery. Compared with other fast-charging cathode materials, the method has the advantages of simple process flow, low cost and easy realization of equipment. The prepared material has the advantages of increasing the interlayer spacing and the surface micropores, not changing the layered structure of the material, increasing the migration channel of lithium ions, limiting the growth of lithium dendrites and reducing the migration resistance of the lithium ions under high current.
Description
Technical Field
The invention belongs to the field of quick charge of lithium ion batteries, and particularly relates to a preparation method of a negative electrode of a lithium ion battery capable of being used for quick charge.
Background
With the development of the information age, the rhythm of our life becomes faster and faster. The realization of the quick charging of the battery brings great convenience to people. Therefore, the fast-charging type lithium ion battery has gained more and more attention, especially, with respect to the electric vehicle. However, the realization of fast charging of lithium ion batteries still faces many problems, the battery polarization is serious, and the negative electrode material is a key factor for limiting the performance. Therefore, the selection and preparation of a proper anode material are the key points for realizing the quick charge of the lithium ion battery.
Li4Ti5O12The material is a spinel structure, has small lattice constant change and small volume change (less than 1 percent), is a good zero-strain material, has no solid electrolyte interface film (SEI film) in the working process of a battery, and is the most studied material in the aspect of the fast-charging lithium ion battery at present. But the platform voltage is lower, the capacity is small, and the energy density of a battery system is reduced. The porous hard carbon has certain effect in the application aspect of the quick-charging lithium ion battery, but the preparation cost is higher. Graphite anodes are low cost, high platform, high energy density and bulk density, and are still the most commercially used anode materials. Therefore, modification research is carried out on the graphite negative electrode material to meet the quick charging conditionHas important significance.
However, the graphite material used for the fast-charging lithium ion battery has many problems, especially the diffusion rate of lithium ions in the graphite negative electrode is very low, so that the polarization of the battery is serious in a large-current charging state, and lithium is easy to separate on the surface of the negative electrode. And the interlayer spacing of the layered graphite material is increased, the porosity is increased, the transmission channel of lithium ions can be increased, the migration resistance is reduced, and the rapid migration of the lithium ions under the action of large current is facilitated. Meanwhile, the porous structure on the surface of the negative electrode can effectively hinder the growth of lithium dendrites. At present, the method for processing graphite capable of being rapidly charged is mainly KOH activation corrosion, and a multi-channel structure is mainly formed by a method of activating a specific surface area by KOH corrosion and then sintering at high temperature, so that the distance between graphite layers is increased, and nano micropores are generated in the material. The graphite material treated by the method has better quick-charging performance. However, the method has long reaction period, needs vacuum calcination, consumes more energy and selects higher raw material cost.
Disclosure of Invention
The invention aims to provide a preparation method of a negative electrode of a lithium ion battery, which has the advantages of simple process, low cost, simple equipment and contribution to industrialization and can be used for quick charging. Therefore, the following technical scheme is proposed:
a graphite cathode for a quick-charging lithium ion battery is prepared by oxidizing and corroding graphite material and embedding the graphite material between ion layers to increase the distance between the treated graphite material layers and form nano-micropores.
In a further improvement of the above aspect, the method for preparing a graphite negative electrode for rapid charging includes the steps of:
step 1): taking a certain amount of graphite material, putting an oxidizing acid solution mixed according to a certain proportion and an interlayer embedded ionic salt mixed solution into the graphite material under a certain temperature condition, and carrying out magnetic stirring reaction for a certain time;
step 2): and (3) washing the mixture reacted in the step (1) by using a weak base solution to be neutral, washing by using deionized water, filtering and drying.
In addition, the step 1) can also be further improved by the following steps: adding a certain amount of graphite material into the oxidizing acid solution, magnetically stirring in a water bath kettle at a certain temperature for a period of time, adding the solution of the embedded ionic salt solution, stirring and mixing for 3-8h, and standing.
In a further improvement of the above solution, the solution of intercalating ionic salts in step 1) is one or more of a neutral or weakly acidic alkali metal ion salt having an ionic radius larger than that of lithium ions.
In a further improvement of the above scheme, the ion-embedding salt solution is one or more of a potassium nitrate solution, a sodium nitrate solution, a potassium chloride solution, a sodium chloride solution, a potassium carbonate solution, a sodium acetate solution and a potassium acetate solution, and preferably one of a potassium nitrate solution and a potassium chloride solution.
The scheme is further improved, the reaction temperature in the oxidation environment in the step 1) is 10-40 ℃, and the reaction time is 0.1-1 hour.
The proposal is further improved, the mixing ratio of the oxidizing acid solution to the intercalation ionic salt solution in the step 1) is 0.1 to 0.5, and the mass ratio of the graphite material to the intercalation ionic salt solution is 0.2 to 4.
In a further improvement of the scheme, the weak alkaline washing liquid in the step 2) is a weak alkaline solution of alkali metal ions or NH4+Ionic alkali solutions, preferably potassium hydroxide solutions.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention treats the layered graphite by a method of intercalation of interlayer ions under acid corrosion and oxidizing conditions, and is used for the negative electrode material of the quick-charging lithium ion battery. The layered graphite is put into an acidic mixed solution with a certain concentration and a certain oxidability, the temperature is controlled to be about 25-35 ℃, and after being mixed for a certain time, the layered graphite is filtered and washed. The porous graphite material with larger interlayer spacing is obtained by the corrosion of the oxidizing acid and the action of the embeddable ions, so that the graphite material has the advantages of increasing the migration channel of lithium ions, limiting the growth of lithium dendrites and reducing the migration resistance of the lithium ions under large current, the risk of short circuit of the lithium ion battery caused by the penetration of the lithium dendrites on the diaphragm is avoided, and the safety of the lithium ion battery is favorably improved.
(1) Compared with other fast-charging cathode materials, the cathode of the lithium ion battery prepared by the invention does not contain a binder, so that the specific gravity of the cathode material is higher; because the negative electrode materials are not blocked by insulating substances, the overall conductivity of the negative electrode of the lithium ion battery is correspondingly improved; the preparation method of the lithium ion battery cathode provided by the invention is simple to operate and low in cost. Simple preparation process, cheap raw materials, low cost, simple equipment and processed materials.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.
Example 1
The embodiment provides a preparation method of a graphite cathode for a quick-charging lithium ion battery, which comprises the following steps:
(1) preparing 40ml of 10% dilute nitric acid solution as an oxidant and a corrosive agent, adding 20ml of 20% potassium nitrate solution, fully mixing the two solutions, adding 40g of graphite material, and magnetically stirring for 0.5h in a 30 ℃ water bath kettle;
(2) and (3) filtering the mixture reacted in the step (1), washing the mixture to be neutral by using a potassium hydroxide solution, washing the mixture by using deionized water, filtering and drying the mixture to obtain the target product porous expandable graphite.
Example 2
The embodiment provides a preparation method of a graphite cathode for a quick-charging lithium ion battery, which comprises the following steps:
(1) preparing 40ml of 10% dilute nitric acid solution as an oxidant and a corrosive agent, adding 40g of graphite material, magnetically stirring for 0.5h in a water bath kettle at the temperature of 30 ℃, then adding 20ml of 20% potassium carbonate solution, stirring and mixing for 3-8h, and standing;
(2) and (3) filtering the mixture reacted in the step (1), washing the mixture to be neutral by using a potassium hydroxide solution, washing the mixture by using deionized water, filtering and drying the mixture to obtain the target product porous expandable graphite.
Example 3
The embodiment provides a preparation method of a graphite cathode for a quick-charging lithium ion battery, which comprises the following steps:
(1) preparing 40ml of 10% diluted hydrochloric acid solution as a corrosive agent, adding 5ml of hydrogen peroxide as an oxidant, adding 20ml of 20% potassium nitrate solution to provide intercalation ions of the graphite material, fully and uniformly mixing the solutions, adding 40g of the graphite material, and magnetically stirring for 0.5h in a 30 ℃ water bath kettle;
(2) and (3) filtering the mixture reacted in the step (1), washing the mixture with ammonia water to be neutral, then washing the mixture with deionized water, filtering and drying the mixture to obtain the target product porous expandable graphite.
Example 4
The embodiment provides a preparation method of a graphite cathode for a quick-charging lithium ion battery, which comprises the following steps:
(1) preparing 40ml of 10% dilute hydrochloric acid solution as a corrosive agent, adding 5ml of hydrogen peroxide as an oxidant, fully and uniformly mixing the solution, adding 40g of graphite material, magnetically stirring in a 30 ℃ water bath kettle for 0.5h, then adding 20ml of 20% potassium nitrate solution to provide intercalation ions of the graphite material, stirring in the water bath kettle for 3-8h, and then standing;
(2) and (3) filtering the mixture reacted in the step (1), washing the mixture with an aqueous alkali solution of ammonia water to be neutral, washing the mixture with deionized water, filtering and drying the mixture to obtain the target product porous expandable graphite.
It should be understood by those skilled in the art that the above embodiments are only for illustrating the present invention and are not to be used as a limitation of the present invention, and that changes and modifications to the above embodiments are within the scope of the claims of the present invention as long as they are within the spirit and scope of the present invention.
Claims (5)
1. A preparation method of a graphite cathode for a quick charging lithium ion battery is characterized by comprising the following steps: oxidizing and corroding the graphite material and carrying out ion interlayer embedding treatment to increase the distance between the treated graphite material layers and form nano micropores; the preparation method comprises the following steps:
step 1): taking a certain amount of graphite material, putting the graphite material into a mixed solution of an oxidizing acid solution and an interlayer embedded ionic salt which are mixed according to a certain proportion under a certain temperature condition, and carrying out magnetic stirring reaction for a certain time;
step 2): washing the mixture reacted in the step 1) to be neutral by using a weak base solution, washing by using deionized water, filtering and drying to obtain a target product, namely porous expandable graphite;
the oxidizing acid solution is a dilute nitric acid solution with the concentration of 10% or a dilute hydrochloric acid solution with the concentration of 10% added with hydrogen peroxide;
the temperature conditions in step 1) are reaction temperature: magnetic stirring at 10-40 deg.c for 0.1-1 hr.
2. The method of claim 1 for preparing a graphite negative electrode for a rapid-charge lithium ion battery, wherein the method comprises the following steps: the intercalation ionic salt solution in step 1) is one or more of neutral or weakly acidic alkali metal ion salts having an ionic radius larger than that of lithium ions.
3. The method of claim 2 for preparing a graphite negative electrode for a rapid-charge lithium ion battery, wherein the method comprises the following steps: the embedded ionic salt solution is one or more of potassium nitrate solution, sodium nitrate solution, potassium chloride solution, sodium chloride solution, potassium carbonate solution, sodium acetate solution and potassium acetate solution.
4. The method for preparing a graphite negative electrode for a rapid-charging lithium ion battery according to claim 1 or 2, characterized in that: the mixing ratio of the oxidizing acid solution to the embedded ion salt solution in the step 1) is 0.1-0.5, and the mass ratio of the graphite material to the embedded ion salt solution is 0.2-4.
5. The method of preparing a graphite negative electrode for a rapid-charging lithium ion battery according to claim 1, characterized in that: step 2) medium and weak alkaline washingThe washing liquid is weak alkali solution or NH of alkali metal ions4 +An ionic alkali solution.
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| CN115974114B (en) * | 2023-03-18 | 2023-07-14 | 河北坤天新能源股份有限公司 | Quick-charging graphite composite material and preparation method thereof |
| CN116281996A (en) * | 2023-03-27 | 2023-06-23 | 青岛洛唯新材料有限公司 | Preparation method of high-interlayer-spacing graphite, negative electrode and lithium battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102701194A (en) * | 2012-06-19 | 2012-10-03 | 上海交通大学 | Method for processing graphite oxide |
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| GB1318652A (en) * | 1970-09-03 | 1973-05-31 | Tatabanyai Aluminiumkoho | Process for the preparation of and oxidation-resistant carbon-or graphite-based article |
| CN1141746C (en) * | 2000-09-13 | 2004-03-10 | 中国科学院化学研究所 | Carbon material as negative electrode of Li-ion battery and its preparing process and application |
| CN101246962A (en) * | 2008-03-18 | 2008-08-20 | 浙江大学 | Preparation of modified graphite cathode material of lithium ion secondary battery |
| KR101002566B1 (en) * | 2008-07-29 | 2010-12-17 | 삼성에스디아이 주식회사 | Electrolyte for lithium ion secondary battery and lithium ion secondary battery comprising the same |
| WO2012164577A1 (en) * | 2011-06-03 | 2012-12-06 | Council Of Scientific & Industrial Research | A process for the preparation of kish graphitic lithium-insertion anode materials for lithium-ion batteries |
| CN102263257B (en) * | 2011-06-28 | 2013-08-07 | 中国科学院金属研究所 | High energy flexible electrode material and preparation method thereof and application thereof in storage battery |
| CN103985873B (en) * | 2014-05-19 | 2016-09-28 | 陕西科技大学 | A kind of method improving cathode material of lithium ion battery cyclical stability |
| CN104157863B (en) * | 2014-08-22 | 2016-06-01 | 东莞市长安东阳光铝业研发有限公司 | The preparation method of a kind of microdilatancy graphite cathode material |
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| CN102701194A (en) * | 2012-06-19 | 2012-10-03 | 上海交通大学 | Method for processing graphite oxide |
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