CN112290022B - Lithium ion battery anode lithium supplement additive and preparation method and application thereof - Google Patents
Lithium ion battery anode lithium supplement additive and preparation method and application thereof Download PDFInfo
- Publication number
- CN112290022B CN112290022B CN202011123437.6A CN202011123437A CN112290022B CN 112290022 B CN112290022 B CN 112290022B CN 202011123437 A CN202011123437 A CN 202011123437A CN 112290022 B CN112290022 B CN 112290022B
- Authority
- CN
- China
- Prior art keywords
- lithium
- ion battery
- lithium ion
- supplement additive
- graphene oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
- H01M4/0435—Rolling or calendering
-
- 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
- H01M4/131—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
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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 discloses a lithium ion battery anode lithium supplement additive and a preparation method and application thereof, relating to the technical field of lithium ion batteries and comprising the following steps: adding cobalt salt into the graphene oxide dispersion liquid, and stirring and dissolving to obtain turbid liquid; dropwise adding a urea aqueous solution into the suspension, stirring, and transferring the obtained solution into a hydrothermal kettle for hydrothermal reaction; centrifuging and drying the hydrothermal reaction product, and calcining to obtain a compound of graphene and nano cobaltosic oxide, namely rGO @ Co3O4A complex; under inert atmosphere, rGO @ Co3O4Mixing the compound with stabilized lithium metal powder, and sintering to obtain a pre-lithiation reagent rGO @ Co/Li2And (3) an O complex. The invention prepares rGO @ Li based on conversion reaction2O/Co nanocomposites, Li2The O/Co serving as the nano particles can be attached to the surface of graphene to improve the conductivity, and meanwhile, the nano composite has higher theoretical capacity and excellent lithium supplement performance, and can compensate irreversible Li caused by SEI film formation in the first charge-discharge process+Is lost.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a lithium supplement additive for a lithium ion battery anode and a preparation method and application thereof.
Background
The lithium ion battery as a power supply has a very wide application prospect in the fields of portable electronic products, power automobiles and energy storage, and in order to meet the increasingly urgent requirements of modern society on energy, the energy density and the power density of the lithium ion battery need to be continuously improved. In the first charging process of the lithium ion battery, the decomposition of the electrolyte can occur, a solid electrolyte film (SEI film for short) is formed on the surface of the negative electrode, lithium in the positive electrode material can be consumed in the process, so that the capacity of the lithium ion battery is reduced, the existing graphite negative electrode material has 5-10% of first irreversible lithium loss, and for a high-capacity negative electrode material, the first lithium loss is even higher (the irreversible capacity loss of silicon reaches 15-35%). Recently some researchers have developed a positive lithium supplement technology, i.e. adding a small amount of high capacity material in the positive slurry mixing process, during the charging process, Li+The lithium-ion battery is separated from a high-capacity material, and the irreversible capacity loss of the first charge and discharge is compensated. Studies have shown that nano-sized Li based on conversion reactions2Mixtures of O and metals as pre-lithium additives for positive electrode materials can provide very high specific capacities during first cycling, where Li2The theoretical capacity of the O/Co composite is 724mAh/g, and the nano composite can generate irreversible electrochemical reaction during the first charging process of the battery (4 Li)2O+3Co→8Li++8e-+Co3O4，2Li2O→4Li++4e-+O2) High capacity electrochemically active lithium ions are provided to compensate for active lithium ions consumed at the surface of the negative electrode material. Due to the nanometer Li2The O/Co complex almost loses its original activity after the first charge, and the capacity rapidly decays with the progress of charge and discharge, so that it can hinder Li as an additive+To be transmitted.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a lithium ion battery anode lithium supplement additive and a preparation method and application thereof.
The invention provides a preparation method of a lithium ion battery anode lithium supplement additive, which comprises the following steps:
s1, adding cobalt salt into the graphene oxide dispersion liquid, and stirring and dissolving to obtain a suspension;
s2, dropwise adding the urea aqueous solution into the suspension of S1, stirring, and transferring the obtained solution into a hydrothermal kettle for hydrothermal reaction;
s3, centrifuging and drying the hydrothermal reaction product in S2, and calcining to obtain the compound of graphene and nano cobaltosic oxide, namely rGO @ Co3O4A complex;
s4, under inert atmosphere, mixing rGO @ Co3O4Mixing the compound with stabilized lithium metal powder, and sintering to obtain a pre-lithiation reagent rGO @ Co/Li2And (3) an O complex.
In the invention S1, the graphene oxide dispersion liquid is obtained by ultrasonically dispersing graphene oxide in a solvent, wherein the solvent can be an ethanol water solution.
In the invention S2, the urea aqueous solution is dripped into the suspension of S1, the suspension is stirred under the action of ultrasound in the dripping process, the suspension is continuously stirred for 3 hours after the dripping process is finished, and the obtained solution is transferred into a hydrothermal kettle for hydrothermal reaction.
Preferably, the graphene oxide is one-dimensional or two-dimensional graphene oxide, preferably one or more of graphene oxide nanoribbons, graphene oxide nanotubes, graphene oxide nanowires, and graphene oxide nanosheets; preferably, the cobalt salt is one or more of cobalt nitrate, cobalt sulfate and cobalt acetate.
In the invention, the mass concentration of graphene oxide in the graphene oxide dispersion liquid is 0.0001-0.01 g/mL; the concentration of the urea is 1-6 mol/L.
Preferably, the mass ratio of the graphene oxide to the cobalt salt is 0.05-3: 100, respectively; preferably, the molar ratio of urea to cobalt salt is 1-4: 1; preferably, rGO @ Co3O4The molar ratio of the composite to the stabilized lithium metal powder is 1:5 to 10.
Preferably, in S2, the hydrothermal reaction temperature is 150-180 ℃ and the reaction time is 10-18 h.
Preferably, in S3, the calcination temperature is 400-500 ℃ and the calcination time is 3-8 h.
Preferably, in S4, the sintering is a two-stage sintering, the first stage: the sintering temperature is 170-185 ℃, the sintering time is 15-30 min, and the second stage is as follows: the sintering temperature is 200-210 ℃, and the sintering time is 2-3 h; preferably, the sintering is carried out using a rotary furnace.
In the invention, the rotating speed of the rotary furnace is 1-10 rpm/min.
The invention also provides a lithium supplement additive for the lithium ion battery anode prepared by the method.
The invention also provides the application of the lithium ion battery anode lithium supplement additive in lithium ion battery anode lithium supplement, which is to uniformly mix the lithium ion battery anode lithium supplement additive with an anode active material, a conductive agent, a binder and a solvent in the anode pulping process, and then prepare an anode piece through coating, rolling and drying.
Preferably, the mass percentage of the lithium supplement additive for the positive electrode of the lithium ion battery is 0.5-5% by taking the lithium supplement additive for the positive electrode of the lithium ion battery, the positive electrode active material, the conductive agent and the binder as a whole.
In the invention, the lithium ion battery anode lithium supplement additive, the anode active material, the conductive agent and the binder are taken as a whole, and the mass percentage of each component is as follows: 75-97.5% of positive electrode active material, 1-10% of conductive agent, 1-10% of binder and 0.5-5% of lithium supplement additive for the positive electrode of the lithium ion battery.
Preferably, the positive active material is ternary nickel cobalt lithium manganate LiNixCoyMn1-x-yO2X is more than or equal to 0 and less than or equal to 1; preferably, the conductive agent is one or more of carbon black, acetylene black, carbon nanotubes and graphene.
Has the advantages that: the invention prepares rGO @ Li based on conversion reaction2The O/Co nano composite is prepared through preparing Co3O4Composite with graphene, making Co3O4Uniformly attaching the composite material on the surface of graphene, and then mixing and sintering the composite material and stabilized lithium metal powder to form uniform particles on the surface of grapheneDistributed Li2O/Co nanoparticles, resulting in a composite with good electrical conductivity. The rGO @ Li2The O/Co nano composite has higher theoretical capacity, can contribute a large amount of lithium in the first charging process, provides high electrochemical activity lithium ions for compensating the active lithium ions consumed on the surface of the negative electrode material, and has excellent lithium supplementing performance because lithium intercalation reaction can not occur in the discharging process. rGO @ Li2The O/Co compound as a high lithium-supplying material can compensate irreversible Li caused by SEI film formation in the first charge-discharge process+When Li is lost2After the O/Co nano composite fails to work during first charging, the graphene still has good conductivity and can serve as a conductive agent to promote Li+Of the network element. The preparation method of the compound is simple, the raw materials are rich, the energy consumption and the production cost are low, the production process is safe and reliable, the large-scale production is easy, the environment stability is good, and the compound is compatible with the production process of a commercial battery.
Drawings
Fig. 1 is a graph of the rate at 0.2C, 0.33C, 1C, 0.2C and a graph of the 50-cycle at 1C of a battery assembled by using the positive electrode sheets of the lithium ion batteries prepared in example 1 of the present invention and comparative example 1.
Detailed Description
The technical means of the present invention will be described in detail below with reference to specific examples.
Example 1
1. Preparing a lithium ion battery anode lithium supplement additive: 0.1g of graphene oxide was ultrasonically dispersed in 50ml of an aqueous ethanol solution (V)Ethanol:VWater (W)1:1) to obtain a graphene oxide dispersion liquid, adding 100g of cobalt nitrate into the graphene oxide dispersion liquid, and fully stirring and dissolving to obtain a suspension A. Then preparing 100ml of urea aqueous solution with the concentration of 6mol/L, namely solution B, slowly dropwise adding the solution B into the turbid liquid A, stirring while carrying out ultrasonic treatment in the dropwise adding process to obtain solution C, continuously stirring for 3 hours, adding the obtained solution into a hydrothermal kettle, reacting for 14 hours at 150 ℃, taking out, centrifuging, drying, and calcining at high temperature of 400 ℃ for 8 hours to obtain the compound of graphene and nano cobaltosic oxideCompound, rGO @ Co for short3O4A complex; under the argon atmosphere, rGO @ Co3O4Uniformly mixing the compound and the stabilized lithium metal powder according to a molar ratio of 1:5, putting the mixture into a rotary furnace, firstly preserving heat at 185 ℃ for 20min, then heating to 200 ℃ and preserving heat for 3h (wherein the rotating speed of the rotary furnace is 5rpm/min), and obtaining rGO @ Co/Li2And (3) an O complex.
2. Preparing the anode of the lithium ion battery: mixing the rGO @ Co/Li prepared above2O composite and positive electrode active material LiNi0.8Co0.1Mn0.1O2Mixing conductive agent carbon black and binder PVDF according to the mass ratio of 2:96:1:1 to prepare slurry, controlling the solid content of the slurry to be 68%, then coating the slurry on an aluminum foil current collector, drying, rolling, and drying in vacuum at 80 ℃ for 12h to obtain the lithium ion battery positive pole piece, controlling the compaction density of the pole piece to be 3.2g/cm3。
Example 2
1. Preparing a lithium ion battery anode lithium supplement additive: compared with step 1 in example 1, the only difference is that: the mass ratio of the graphene oxide to the cobalt nitrate is 0.2:100, rGO @ Co3O4The molar ratio of the composite to the stabilized lithium metal powder was 1:8, and the other conditions and steps were the same as in step 1 of example 1;
2. preparing the anode of the lithium ion battery: the experimental procedure and conditions were the same as described in step 2 of example 1.
Example 3
1. Preparing a lithium ion battery anode lithium supplement additive: compared with step 1 in example 1, the only difference is that: the mass ratio of the graphene oxide to the cobalt nitrate is 0.3:100, rGO @ Co3O4The molar ratio of the composite to the stabilized lithium metal powder was 1:10, and the other conditions and steps were the same as in step 1 of example 1;
2. preparing the anode of the lithium ion battery: the experimental procedure and conditions were the same as described in step 2 of example 1.
Example 4
1. Preparing a lithium ion battery anode lithium supplement additive: compared with step 1 in example 1, the only difference is that: water (W)The reaction temperature of the hot kettle is 180 ℃, the reaction time is 10 hours, the calcining temperature is 500 ℃, and the calcining time is 3 hours; mixing rGO @ Co3O4Uniformly mixing the compound and the stabilized lithium metal powder according to a molar ratio of 1:10, firstly preserving heat at 170 ℃ for 30min, and then heating to 210 ℃ and preserving heat for 2h (wherein the rotating speed of a rotary furnace is 7 rpm/min); other conditions and steps were the same as in step 1 of example 1;
2. preparing the anode of the lithium ion battery: the rGO @ Co/Li prepared above is mixed2O composite and positive electrode active material LiNi0.8Co0.1Mn0.1O2Mixing conductive agent carbon black and binder PVDF according to the mass ratio of 4:94:1:1 to prepare slurry, controlling the solid content of the slurry to be 66%, then coating the slurry on an aluminum foil current collector, drying, rolling, and drying in vacuum at 80 ℃ for 12h to obtain the lithium ion battery positive pole piece, controlling the compaction density of the pole piece to be 3.15g/cm3。
Example 5
1. Preparing a lithium ion battery anode lithium supplement additive: compared with step 1 in example 1, the only difference is that: the reaction temperature of the hydrothermal kettle is 160 ℃, the reaction time is 15h, the calcination temperature is 450 ℃, and the calcination time is 5 h; mixing rGO @ Co3O4Uniformly mixing the compound and the stabilized lithium metal powder according to a molar ratio of 1:9, firstly preserving heat at 180 ℃ for 15min, and then heating to 205 ℃ and preserving heat for 2.5h (wherein the rotating speed of a rotary furnace is 10 rpm/min); other conditions and steps were the same as in step 1 of example 1;
2. preparing the anode of the lithium ion battery: the experimental procedures and conditions were the same as those described in step 2 of example 4.
Comparative example 1
Preparing the anode of the lithium ion battery: LiNi serving as a positive electrode active material0.8Co0.1Mn0.1O2Mixing conductive agent carbon black and binder PVDF according to a mass ratio of 98:1:1 to prepare slurry, controlling the solid content of the slurry to be 68%, then coating the slurry on an aluminum foil current collector, drying, rolling, and vacuum drying at 80 ℃ for 12h to obtain the lithium ion battery positive electrode piece, and controlling the compacted density of the electrode piece to be 3.2g/cm3。
The positive electrode pieces in example 1 and comparative example 1 were used as positive electrodes, graphite as negative electrodes, and 1mol/L LiPF as electrolyte, respectively6(solute)/EC + DEC + EMC (solvent), in a N/P ratio of 1.15, was assembled into a monolithic pouch cell and tested for electrochemical performance. The first charge and discharge capacity, first coulombic efficiency, multiplying power and cycle data are shown in table 1, wherein multiplying power curves (0.2C, 0.33C, 1C, 0.2C) and 50-week cycle curves at 1C are shown in fig. 1.
TABLE 1 electrochemical data for example 1 and comparative example 1
As can be seen from table 1 and fig. 1, the electrochemical performance of the cell of example 1 is significantly better than that of comparative example 1.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A preparation method of a lithium ion battery anode lithium supplement additive is characterized by comprising the following steps:
s1, adding cobalt salt into the graphene oxide dispersion liquid, stirring and dissolving to obtain turbid liquid, wherein the mass ratio of the graphene oxide to the cobalt salt is 0.05-3: 100;
s2, dropwise adding the urea aqueous solution into the suspension of the S1, stirring, transferring the obtained solution into a hydrothermal kettle for hydrothermal reaction, wherein the temperature of the hydrothermal reaction is 150-180 ℃, the reaction time is 10-18 h, and the molar ratio of urea to cobalt salt is 1-4: 1;
s3, centrifuging and drying the hydrothermal reaction product in S2, and calcining to obtain the compound of graphene and nano cobaltosic oxide, namely rGO @ Co3O4Calcining the compound at 400-500 ℃ for 3-8 h;
s4, under inert atmosphere, mixing rGO @ Co3O4Mixing the compound with stabilized lithium metal powder, and sintering to obtain a pre-lithiation reagent rGO @ Co/Li2O compound, sintering is two-stage sintering, wherein the first stage is as follows: the sintering temperature is 170-185 ℃, the sintering time is 15-30 min, and the second stage is as follows: the sintering temperature is 200-210 ℃, the sintering time is 2-3 h, rGO @ Co3O4The molar ratio of the composite to the stabilized lithium metal powder is 1:5 to 10.
2. The method for preparing the lithium ion battery positive electrode lithium supplement additive according to claim 1, wherein the graphene oxide is one-dimensional or two-dimensional graphene oxide.
3. The preparation method of the lithium ion battery positive electrode lithium supplement additive according to claim 2, wherein the graphene oxide is one or more of a graphene oxide nanoribbon, a graphene oxide nanotube, a graphene oxide nanowire and a graphene oxide nanosheet.
4. The preparation method of the lithium ion battery anode lithium supplement additive according to claim 1, wherein the cobalt salt is one or more of cobalt nitrate, cobalt sulfate and cobalt acetate.
5. The method for preparing the lithium ion battery positive electrode lithium supplement additive according to any one of claims 1 to 4, wherein in S4, a rotary furnace is used for sintering.
6. A lithium ion battery positive electrode lithium supplement additive prepared by the method of any one of claims 1-5.
7. The application of the lithium ion battery anode lithium supplement additive in the lithium ion battery anode lithium supplement of claim 6 is characterized in that in the anode pulping process, the lithium ion battery anode lithium supplement additive, an anode active material, a conductive agent, a binder and a solvent are uniformly mixed, and then the anode pole piece is prepared through coating, rolling and drying.
8. The application of the lithium ion battery anode lithium supplement additive in lithium ion battery anode lithium supplement according to claim 7 is characterized in that the mass percentage of the lithium ion battery anode lithium supplement additive is 0.5-5% by taking the lithium ion battery anode lithium supplement additive, an anode active material, a conductive agent and a binder as a whole.
9. The application of the lithium ion battery positive electrode lithium supplement additive in lithium ion battery positive electrode lithium supplement according to claim 7 or 8, characterized in that the positive electrode active material is ternary lithium nickel cobalt manganese LiNixCoyMn1-x-yO2，0＜x＜1。
10. The application of the lithium ion battery positive electrode lithium supplement additive in lithium ion battery positive electrode lithium supplement according to claim 7 or 8 is characterized in that the conductive agent is one or more of carbon black, carbon nano tube and graphene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011123437.6A CN112290022B (en) | 2020-10-20 | 2020-10-20 | Lithium ion battery anode lithium supplement additive and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011123437.6A CN112290022B (en) | 2020-10-20 | 2020-10-20 | Lithium ion battery anode lithium supplement additive and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112290022A CN112290022A (en) | 2021-01-29 |
| CN112290022B true CN112290022B (en) | 2022-07-05 |
Family
ID=74423330
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011123437.6A Active CN112290022B (en) | 2020-10-20 | 2020-10-20 | Lithium ion battery anode lithium supplement additive and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112290022B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115881960A (en) * | 2021-09-30 | 2023-03-31 | 华为技术有限公司 | Positive electrode additive, preparation method and application thereof, secondary battery and terminal equipment |
| CN114335545B (en) * | 2022-01-06 | 2024-01-26 | 天能帅福得能源股份有限公司 | Lithium ion battery lithium supplementing additive and preparation method thereof |
| CN115353097B (en) * | 2022-08-17 | 2023-12-19 | 上海兰钧新能源科技有限公司 | Graphene nanotube, positive electrode slurry, positive electrode sheet, battery cell and electronic device |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103985561A (en) * | 2014-05-28 | 2014-08-13 | 中国工程物理研究院化工材料研究所 | Graphene in-situ load needle-shaped Co3O4 composite electrode material and manufacturing method thereof |
| CN104263317A (en) * | 2014-09-26 | 2015-01-07 | 厦门大学 | Method for synthesizing cobalt oxide/graphene composite wave-absorbing material |
| CN104785266A (en) * | 2015-03-23 | 2015-07-22 | 上海电力学院 | Preparation method of nanometer cobalt oxide/graphene composite material |
| CN105702913A (en) * | 2014-11-27 | 2016-06-22 | 比亚迪股份有限公司 | Positive electrode and preparation method therefor, and lithium secondary battery |
| CN107221650A (en) * | 2017-07-07 | 2017-09-29 | 安普瑞斯（无锡）有限公司 | One kind mends lithium additive and preparation method thereof |
| CN107819113A (en) * | 2017-09-22 | 2018-03-20 | 深圳市比克动力电池有限公司 | One kind mends lithium additive and its preparation method and application |
| CN108232343A (en) * | 2018-01-04 | 2018-06-29 | 中南大学 | Benefit lithium additive, benefit lithium anode and its preparation and application for lithium ion battery |
| CN108539160A (en) * | 2018-04-04 | 2018-09-14 | 合肥国轩高科动力能源有限公司 | A kind of CoO/rGO compounds and preparation method thereof and purposes |
| CN109786746A (en) * | 2018-12-25 | 2019-05-21 | 深圳市比克动力电池有限公司 | Positive plate, lithium ion cell positive mend lithium material and preparation method thereof |
| CN110176641A (en) * | 2019-06-03 | 2019-08-27 | 哈尔滨工业大学 | A kind of nanometer of LiF/Fe/ graphite anode mends the preparation method and applications of lithium slurry |
| CN111193019A (en) * | 2020-01-13 | 2020-05-22 | 惠州亿纬锂能股份有限公司 | Lithium supplement additive, preparation method thereof and lithium ion battery |
| CN111613759A (en) * | 2020-05-27 | 2020-09-01 | 湖北亿纬动力有限公司 | Diaphragm slurry, preparation method thereof, diaphragm and lithium ion battery |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6350543B2 (en) * | 1999-12-29 | 2002-02-26 | Kimberly-Clark Worldwide, Inc. | Manganese-rich quaternary metal oxide materials as cathodes for lithium-ion and lithium-ion polymer batteries |
| US11398627B2 (en) * | 2015-06-12 | 2022-07-26 | The Board Of Trustees Of The Leland Stanford Junior University | Cathode additives for lithium-ion batteries |
| CN110350194A (en) * | 2018-04-02 | 2019-10-18 | 中国科学院物理研究所 | A kind of benefit lithium slurry and its preparation method and application |
-
2020
- 2020-10-20 CN CN202011123437.6A patent/CN112290022B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103985561A (en) * | 2014-05-28 | 2014-08-13 | 中国工程物理研究院化工材料研究所 | Graphene in-situ load needle-shaped Co3O4 composite electrode material and manufacturing method thereof |
| CN104263317A (en) * | 2014-09-26 | 2015-01-07 | 厦门大学 | Method for synthesizing cobalt oxide/graphene composite wave-absorbing material |
| CN105702913A (en) * | 2014-11-27 | 2016-06-22 | 比亚迪股份有限公司 | Positive electrode and preparation method therefor, and lithium secondary battery |
| CN104785266A (en) * | 2015-03-23 | 2015-07-22 | 上海电力学院 | Preparation method of nanometer cobalt oxide/graphene composite material |
| CN107221650A (en) * | 2017-07-07 | 2017-09-29 | 安普瑞斯（无锡）有限公司 | One kind mends lithium additive and preparation method thereof |
| CN107819113A (en) * | 2017-09-22 | 2018-03-20 | 深圳市比克动力电池有限公司 | One kind mends lithium additive and its preparation method and application |
| CN108232343A (en) * | 2018-01-04 | 2018-06-29 | 中南大学 | Benefit lithium additive, benefit lithium anode and its preparation and application for lithium ion battery |
| CN108539160A (en) * | 2018-04-04 | 2018-09-14 | 合肥国轩高科动力能源有限公司 | A kind of CoO/rGO compounds and preparation method thereof and purposes |
| CN109786746A (en) * | 2018-12-25 | 2019-05-21 | 深圳市比克动力电池有限公司 | Positive plate, lithium ion cell positive mend lithium material and preparation method thereof |
| CN110176641A (en) * | 2019-06-03 | 2019-08-27 | 哈尔滨工业大学 | A kind of nanometer of LiF/Fe/ graphite anode mends the preparation method and applications of lithium slurry |
| CN111193019A (en) * | 2020-01-13 | 2020-05-22 | 惠州亿纬锂能股份有限公司 | Lithium supplement additive, preparation method thereof and lithium ion battery |
| CN111613759A (en) * | 2020-05-27 | 2020-09-01 | 湖北亿纬动力有限公司 | Diaphragm slurry, preparation method thereof, diaphragm and lithium ion battery |
Non-Patent Citations (3)
| Title |
|---|
| "High-capacity battery cathode prelithiation to offset initial lithium loss";Sun Yongming et al.;《NATURE ENERGY》;20160111;第1卷;第1页第1段到第7页第2段 * |
| 锂离子电池预锂化技术的研究;孙仲振等;《化工管理》;20200901(第25期);全文 * |
| 锂离子电池预锂化技术的研究现状;朱亮等;《电池》;20180625(第03期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112290022A (en) | 2021-01-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105742635B (en) | A kind of tin ash/graphene/carbon composite material and preparation method thereof | |
| CN112290022B (en) | Lithium ion battery anode lithium supplement additive and preparation method and application thereof | |
| CN101937985B (en) | Graphene/titanium dioxide lithium ion battery cathode material and preparation method | |
| CN105762337B (en) | A kind of silicon/graphene/carbon fiber composite negative material and preparation method thereof | |
| CN108598444B (en) | Vanadium trioxide/graphene composite negative electrode material of lithium ion battery and preparation method | |
| CN105720251A (en) | Antimony sulfide based composite material of sodium-ion battery and preparation method of antimony sulfide based composite material | |
| CN104966824A (en) | Nitrogen-doped porous carbon sphere and cobaltous oxide nano-composite anode material based on chitosan and derivatives thereof and preparation method thereof | |
| CN101420034A (en) | Carbon coated granularity controllable spherical lithium ferric phosphate composite positive pole material and preparation method thereof | |
| CN113725432B (en) | ZIF-67 and preparation method of cobalt selenide/carbon electrode material derived from ZIF-67 | |
| CN108658119B (en) | Method for preparing copper sulfide nanosheet and compound thereof by low-temperature vulcanization technology and application | |
| CN103280570B (en) | Preparation method of micron-order single-crystal nickel lithium manganate anode material | |
| CN102104143A (en) | Hydrothermal synthesis method of composite material for high-performance power battery | |
| CN102311109B (en) | Method for preparing LiFePO4/C composite cathode material by continuous reaction | |
| CN107394178B (en) | Cobalt carbonate/graphene composite material for sodium-ion battery cathode and preparation method and application thereof | |
| CN103972497A (en) | Co2SnO4/C nano-composite negative electrode material for lithium ion battery, preparation and application of Co2SnO4/C nano-composite negative electrode material | |
| CN112357956B (en) | Carbon/titanium dioxide coated tin oxide nanoparticle/carbon assembled mesoporous sphere material and preparation and application thereof | |
| CN108448072B (en) | Preparation method and application of two-dimensional antimony trioxide nanosheet/reduced graphene oxide aerogel based composite electrode material | |
| CN103531789A (en) | Iron oxide-carbon nanotube ternary composite material and preparation method thereof | |
| CN108899520B (en) | Globose Na3V2O2(PO4)2F-GO nano composite material and preparation method and application thereof | |
| CN108358249B (en) | A kind of preparation method of anode material for lithium-ion batteries nickel molybdate | |
| CN109980221A (en) | A kind of anode material for high-voltage lithium ion and its preparation method and application | |
| CN112186166A (en) | Molybdenum/cobalt oxide-carbon composite material and preparation method thereof, lithium ion battery negative electrode piece and lithium ion battery | |
| CN112028045A (en) | Conductive lithium iron phosphate and preparation method and application thereof | |
| CN111261866B (en) | Preparation method of ZnO/C nano composite microsphere material with capsule structure | |
| CN101728524A (en) | Lithium ion battery/capacitor electrode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |