CN112054202A - High-energy high-rate lithium battery positive electrode additive, preparation method thereof and positive plate containing positive electrode additive - Google Patents
High-energy high-rate lithium battery positive electrode additive, preparation method thereof and positive plate containing positive electrode additive Download PDFInfo
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Abstract
The invention discloses a high-energy high-rate lithium battery positive electrode additive, a preparation method thereof and a positive electrode plate containing the positive electrode additive, wherein expanded graphite is used as a carbon source raw material, lithium carbonate is used as powder, and the mass ratio of lithium carbonate: the expanded graphite is 1: 1-1: 10, and preparing the lithium carbonate particles coated with the carbon nano particles by adopting a mechanical ball milling method, wherein the particle size is about 20-100 nm. Taking carbon nano-coated lithium carbonate particles as a positive electrode additive, wherein the positive electrode additive comprises the following components in percentage by mass: conductive agent: the adhesive is 100: 0.1: 0.5-100: 1.5:2, and preparing the positive plate. The battery composed of the positive plate has a safe overcharge protection function, low internal resistance and no negative influence on the circulation function of the battery.
Description
Technical Field
The invention relates to the technical field of high-energy high-rate charge and discharge lithium batteries, in particular to a positive electrode additive of a high-energy high-rate lithium battery, a preparation method of the positive electrode additive and a positive plate containing the positive electrode additive.
Background
The lithium ion secondary battery has the advantages of high working voltage, high specific energy, more recycling times, long storage time and the like, is widely applied to portable electronic equipment such as mobile phones, digital cameras, portable computers and the like, and also has wide application in electric vehicles, electric bicycles and other vehicles, wherein the electric vehicles have stricter requirements on the safety performance of the lithium ion secondary battery.
The lithium ion secondary battery, which is generally used as a driving power source for electric vehicles, employs safety measures such as: 1, a safety valve for explosion prevention; and 2, the lithium ion secondary battery protection device is provided with a pressure detection type current blocking device, the current blocking device is started when the lithium ion secondary battery generates abnormal internal quick gas generation, and the lithium ion secondary battery is prevented from thermal runaway by blocking current, so that safety accidents are avoided.
In order to enable the current blocking device to monitor the health state of the lithium ion secondary battery more sensitively and improve the overcharge resistance of the lithium ion secondary battery, in the prior art, lithium carbonate is generally added into a positive plate as an overcharge gas generation additive, and the lithium carbonate is decomposed when the working voltage of the lithium ion secondary battery reaches a certain degree, so that carbon dioxide is generated to start the current blocking device, and the safety of the lithium ion secondary battery is ensured. However, the introduction of the non-conductive lithium carbonate causes the internal resistance of the positive plate to increase, thereby affecting the overall performance of the battery; in addition, lithium carbonate may participate in some side reactions under some specific conditions, which may also affect the overall performance of the battery, for example, active oxygen released from the positive active material may generate heat by side reaction with lithium carbonate at high temperature, and the generated heat may in turn accelerate the temperature rise of the entire battery.
Disclosure of Invention
In order to overcome the disadvantages and shortcomings of the prior art, particularly, aiming at reducing the impedance of the positive plate and ensuring that the overall performance of the battery is not affected on the basis of protection obtained by overcharge, the invention aims to provide a positive electrode additive and a positive plate thereof.
The technical scheme adopted by the invention is as follows: the positive electrode additive is lithium carbonate particles partially or completely coated by carbon particles.
The lithium carbonate has the particle size range of 20-100 nm.
The carbon particles of the high-energy high-rate lithium battery positive electrode additive are 600-mesh expanded graphite.
The high-energy high-rate lithium battery positive electrode additive comprises, by mass, 1% of lithium carbonate and expanded graphite: 1-1: 10.
the preparation method of the positive electrode additive for the high-energy high-rate lithium battery comprises the following steps: and mixing the lithium carbonate and the expanded graphite, and mechanically milling for 8-10 hours to prepare the lithium carbonate particles coated by the carbon nano particles.
A high-energy high-rate lithium battery positive plate comprises the positive electrode additive component.
A preparation method of a high-energy high-rate lithium battery positive plate comprises the following steps: the positive electrode additive described in any one of the above: conductive agent: the adhesive is 100: 0.1: 0.5-100: 1.5:2, mixing the materials in proportion, gradually diluting the mixture by using N-methyl pyrrolidone under stirring to obtain positive electrode slurry, and coating, drying at 90-100 ℃ and rolling the slurry to obtain the target positive electrode sheet.
According to the preparation method of the high-energy high-rate lithium battery positive plate, the mass of the positive electrode additive is 0.1-10% of that of the positive electrode active material, and the positive electrode active material is one or more of lithium metal oxide with a layered structure, lithium-free metal oxide, lithium metal oxide with a spinel structure, lithium metal phosphate, lithium metal fluoride sulfate and lithium metal vanadate.
The high-energy high-rate lithium battery positive electrode additive and the preparation method of the positive electrode plate thereof are characterized in that the mass of the positive electrode additive is 0.1-10% of that of the positive electrode active material. The energy density of the positive plate can be reduced due to the fact that the positive additive is too high in mass, the charging loop cannot be cut off timely when the lithium ion secondary battery is overcharged and abused due to the fact that the positive additive is too low in mass, and thermal runaway of the lithium ion secondary battery cannot be effectively controlled. Preferably, the mass of the positive electrode additive is 0.2-0.6% of the mass of the positive electrode active material
According to the preparation method of the high-energy high-rate lithium battery positive plate, the lithium metal oxide with the layered structure is selected from Lithium Cobaltate (LCO), a nickel-cobalt-manganese ternary material (NCM) and a nickel-cobalt-aluminum ternary material (NCA); the lithium-free metal oxide is selected from V2O5Or MnO2(ii) a The spinel-structured lithium metal oxide is selected from lithium manganate (LiMn)2O4) (ii) a The lithium metal phosphate is selected from lithium iron phosphate (LFP); the lithium metal fluorinated sulfate is selected from the group consisting of fluorinated lithium cobalt sulfate (LiCoFSO)4) (ii) a The lithium metal vanadate is selected from nickel lithium vanadate (LiNiVO)4)。
According to the preparation method of the high-energy high-rate lithium battery positive plate, the conductive agent is one or more of graphite, acetylene black, conductive carbon black, superconducting carbon black, graphene, carbon nano tubes, conductive fibers, metal powder and an organic conductive polymer; the graphite is selected from natural graphite or artificial graphite; the acetylene black is selected from Ketjen black; the conductive fibers are selected from carbon fibers or metal fibers; the metal powder is selected from copper powder or nickel powder; the organic conductive polymer is selected from polyphenylene derivatives; the adhesive is one or more of polyvinylidene fluoride, polyvinyl alcohol, polyurethane, polyacrylate, butyl rubber, epoxy resin, vinyl acetate resin and chlorinated rubber.
The invention has the following beneficial effects:
according to the invention, small-particle-size lithium carbonate particles are selected as the powder for preparing the positive electrode additive, and the small-particle-size lithium carbonate particles can reduce the interval among positive electrode active material particles and ensure the effective connection among the positive electrode active material particles; and meanwhile, nano carbon with excellent conductivity is adopted to coat the lithium carbonate particles. This approach has the following benefits: firstly, the lithium carbonate serving as a positive electrode overcharge additive can be fully exerted under a specific working voltage (4.8V) to generate gas; and secondly, the close contact among the positive active material particles can be kept, and the deficiency of the conductivity of the lithium carbonate particles is made up by the nano carbon coating with excellent conductivity, so that the impedance of the positive plate can be effectively reduced. The purpose of greatly improving the safety performance of the lithium ion secondary battery is achieved on the basis of not increasing the internal resistance of a pole piece and not influencing the electrical performance of the lithium ion secondary battery; the carbon coating can prevent the side reaction of lithium carbonate.
Drawings
FIG. 1 is a graph showing the comparison of the cycle characteristics of positive electrode sheets obtained in comparative example and example
Detailed Description
Example 1 high-energy high-rate lithium battery positive electrode additive and preparation method of positive electrode plate thereof
Preparation of positive electrode additive
Using 600-mesh expanded graphite as a carbon source raw material, wherein the particle size of lithium carbonate is 25nm, and the proportion of the lithium carbonate to the expanded graphite is 1: 2, mixing; then transferring the powder into a ball milling tank, taking a steel ball with the diameter of 2-5 mm as a grinding ball, and mixing the powder: the ball mass ratio is 1: and (3) performing high-energy ball milling at the ratio of 20, and performing ball milling for 10 hours to obtain lithium carbonate powder coated by the carbon nano particles, wherein the particle size of the obtained lithium carbonate particles coated by the carbon nano particles is about 30 nm.
(II) preparation of Positive plate
The method comprises the following steps of mixing a positive electrode active material NCM532, a positive electrode additive, a conductive agent Keqin black and a binder PVDF according to the mass ratio of 100: 1: 1.5:2, gradually adding N-methyl pyrrolidone until the solid content is 52%, and fully stirring to obtain the anode slurry. And coating the positive electrode slurry on the positive surface and the negative surface of a positive electrode current collector aluminum foil with the thickness of 12 microns, and performing forced air drying, cold pressing and slitting at the temperature of 85 ℃ to obtain a positive plate.
Preparation of positive electrode additive
Using 600-mesh expanded graphite as a carbon source raw material, wherein the particle size of lithium carbonate is 60nm, and the proportion of the lithium carbonate to the expanded graphite is 1: 5, mixing in proportion; then transferring the powder into a ball milling tank, taking a steel ball with the diameter of 2-5 mm as a grinding ball, and mixing the powder: the ball mass ratio is 1: 20, and performing high-energy ball milling for 10 hours to obtain the lithium carbonate powder coated by the carbon nano particles, wherein the particle size is about 65 nm.
(II) preparation of Positive plate
The method comprises the following steps of mixing a positive electrode active material NCM811, a positive electrode additive, a conductive agent Keqin black and a binder PVDF according to the mass ratio of 100: 3: 1.5:2, gradually adding N-methyl pyrrolidone until the solid content is 52%, and fully stirring to obtain the anode slurry. And coating the positive electrode slurry on the positive surface and the negative surface of a positive electrode current collector aluminum foil with the thickness of 12 microns, and performing forced air drying, cold pressing and slitting at the temperature of 85 ℃ to obtain a positive plate.
Example 3 high-energy high-rate lithium battery positive electrode additive and preparation method of positive electrode plate thereof
Preparation of positive electrode additive
Using 600-mesh expanded graphite as a carbon source raw material, wherein the particle size of lithium carbonate is 90nm, and the proportion of the lithium carbonate to the expanded graphite is 1: 10, mixing; then transferring the powder into a ball milling tank, taking a steel ball with the diameter of 2-5 mm as a grinding ball, and mixing the powder: the ball mass ratio is 1: 20, and performing high-energy ball milling for 10 hours to obtain the lithium carbonate powder coated by the carbon nano particles, wherein the particle size is about 95 nm.
(II) preparation of Positive plate
The method comprises the following steps of mixing a positive electrode active material NCA, a positive electrode additive, a conductive agent Keqin black and a binder PVDF according to the mass ratio of 100: 5: 1.5:2, gradually adding N-methyl pyrrolidone until the solid content is 52%, and fully stirring to obtain the anode slurry. And coating the positive electrode slurry on the positive surface and the negative surface of a positive electrode current collector aluminum foil with the thickness of 12 microns, and performing forced air drying, cold pressing and slitting at the temperature of 85 ℃ to obtain a positive plate.
Embodiment 4 high-energy high-rate lithium battery positive electrode additive and preparation method of positive electrode plate thereof
Preparation of positive electrode additive
Using 600-mesh expanded graphite as a carbon source raw material, wherein the particle size of lithium carbonate is 20nm, and the proportion of the lithium carbonate to the expanded graphite is 1: 1, mixing; then transferring the powder into a ball milling tank, taking a steel ball with the diameter of 2-5 mm as a grinding ball, and mixing the powder: the ball mass ratio is 1: and (3) performing high-energy ball milling at the ratio of 20, and performing ball milling for 10 hours to obtain the lithium carbonate powder coated by the carbon nano particles, wherein the particle size of the carbon particles is about 25 nm.
(II) preparation of Positive plate
The positive electrode active material Li2CoO2The composite material comprises a positive electrode additive, a conductive agent Keqin black and a binder PVDF, wherein the mass ratio of the positive electrode additive to the conductive agent Keqin black is 100: 0.6: 1.5:2, gradually adding N-methyl pyrrolidone until the solid content is 52%, and fully stirring to obtain the anode slurry. And coating the positive electrode slurry on the positive surface and the negative surface of a positive electrode current collector aluminum foil with the thickness of 12 microns, and performing forced air drying, cold pressing and slitting at the temperature of 85 ℃ to obtain a positive plate.
Example 5 high-energy high-rate lithium battery positive electrode additive and preparation method of positive electrode plate thereof
Preparation of positive electrode additive
Using 600-mesh expanded graphite as a carbon source raw material, wherein the particle size of lithium carbonate is 35nm, and the proportion of the lithium carbonate to the expanded graphite is 1: 3, mixing in proportion; then transferring the powder into a ball milling tank, taking a steel ball with the diameter of 2-5 mm as a grinding ball, and mixing the powder: the ball mass ratio is 1: and (3) performing high-energy ball milling at the ratio of 20, and performing ball milling for 10 hours to obtain the lithium carbonate powder coated by the carbon nano particles, wherein the particle size of the carbon particles is about 40 nm.
(II) preparation of Positive plate
The positive electrode active material NCM622, the positive electrode additive, the conductive agent Keqin black and the binder PVDF are mixed according to the mass ratio of 100: 0.3: 1.5:2, gradually adding N-methyl pyrrolidone until the solid content is 52%, and fully stirring to obtain the anode slurry. And coating the positive electrode slurry on the positive surface and the negative surface of a positive electrode current collector aluminum foil with the thickness of 12 microns, and performing forced air drying, cold pressing and slitting at the temperature of 85 ℃ to obtain a positive plate.
Comparative example 1
A positive electrode sheet was prepared in accordance with the method of example 1, except that the positive electrode additive was ordinary lithium carbonate (i.e., lithium carbonate without a coating layer).
Comparative example 2
A positive electrode sheet was prepared in accordance with the method of example 2, except that the positive electrode additive was ordinary lithium carbonate (i.e., lithium carbonate without a coating layer).
Comparative example 3
A positive electrode sheet was prepared in accordance with the method of example 3, except that the positive electrode additive was ordinary lithium carbonate (i.e., lithium carbonate without a coating layer).
Comparative example 4
A positive electrode sheet was prepared in accordance with the method of example 4, except that the positive electrode additive was ordinary lithium carbonate (i.e., lithium carbonate without a coating layer).
Comparative example 5
A positive electrode sheet was prepared in accordance with the method of example 5, except that the positive electrode additive was ordinary lithium carbonate (i.e., lithium carbonate without a coating layer).
Comparative example 6
Preparation of positive plate
Mixing a positive electrode active material NCM532, a conductive agent Keqin black and a binder PVDF according to the mass ratio of 100:1.5:2, gradually adding N-methyl pyrrolidone until the solid content is 52%, and fully stirring to obtain positive electrode slurry. And coating the positive electrode slurry on the positive surface and the negative surface of a positive electrode current collector aluminum foil with the thickness of 12 microns, and performing forced air drying, cold pressing and slitting at the temperature of 85 ℃ to obtain a positive plate.
Example 6
The positive plates obtained in examples 1 to 5 and the positive plates obtained in comparative examples 1 to 6 are matched with an artificial graphite material negative plate to be assembled into a 18650 full cell, and after dipping, formation and aging, the performance test processes and test results of examples 1 to 5 and comparative examples 1 to 5 are finally given.
(1) AC internal resistance test of lithium ion secondary battery
The lithium ion secondary battery was charged at 25 ℃ at 1C to a voltage of 4.2V, and then the internal AC resistance thereof was measured. Each group was tested with 4 lithium ion secondary batteries and the average was taken.
(2) Rate capability test of lithium ion secondary battery
The lithium ion secondary battery was charged at 25 ℃ to a voltage of 4.2V at 3C and discharged at 5C to a voltage of 3.0V for 200 cycles. Each group was tested with 4 lithium ion secondary batteries and the average was taken.
(3) Safety performance test of lithium ion secondary battery
The lithium ion secondary battery was charged at a rate of 1C at 25C until the current interrupt device of the lithium ion secondary battery functioned, and the voltage (i.e., overcharge failure voltage) and SOC state (i.e., overcharge failure SOC) of the lithium ion secondary battery at the time of termination of overcharge were obtained. And 4 lithium ion secondary batteries in each group are tested, and the average value is obtained.
As can be seen from table 1, the overcharge failure voltage and the overcharge failure SOC of 1, examples 1 to 5 and comparative examples 1 to 5 of the lithium ion secondary battery were not significantly different, but were significantly reduced compared to the overcharge failure voltage and the overcharge failure SOC of comparative example 6, indicating that, as the positive electrode overcharge additive, both the nanocarbon-coated lithium carbonate of the present invention and the common lithium carbonate can be decomposed in time to generate gas when the lithium ion secondary battery is overcharged, increasing the internal pressure of the battery, and enabling the pressure detection type current blocking device to function, thereby effectively preventing thermal runaway of the lithium ion secondary battery. 2, the internal resistances of examples 1 to 5 and comparative example 6 were comparable and were significantly lower than those of comparative examples 1 to 5, indicating that the introduction of lithium carbonate resulted in a significant increase in the internal resistance of the cell due to its lack of conductivity; compared with common lithium carbonate, the addition of the nano-carbon coated lithium carbonate positive electrode additive does not increase the internal resistance, and the difference of the internal resistance and the internal resistance of the lithium carbonate positive electrode additive is not great, and the nano-carbon coating changes the conductivity of the common lithium carbonate.
TABLE 1 overcharge failure Voltage, failure SOC, AC internal resistance of comparative and example
As can be seen from FIG. 1, after 200 cycles, the capacity retention rates of examples 1-5 and comparative example 6 are not much different, and the capacity remained over 93% after 200 cycles; the capacity retention rates of comparative examples 1-5 were significantly reduced, and the capacity after 200 cycles was less than 77%, indicating that the addition of nanocarbon-coated lithium carbonate according to the present invention had no effect on cycle performance.
Claims (10)
1. The positive electrode additive is characterized in that the positive electrode additive is lithium carbonate particles partially or completely coated by carbon particles.
2. The positive electrode additive for a high-energy high-rate lithium battery as claimed in claim 1, wherein the lithium carbonate has a particle size ranging from 20 to 100 nm.
3. The positive electrode additive for a high-energy high-rate lithium battery as claimed in claim 2, wherein the carbon particles are 600 mesh expanded graphite.
4. The positive electrode additive for a high-energy high-rate lithium battery as claimed in claim 3, wherein the ratio of lithium carbonate to expanded graphite is 1: 1-1: 10.
5. the method for preparing the positive electrode additive for the high-energy high-rate lithium battery as claimed in any one of claims 1 to 4, wherein the method comprises the following steps: and mixing the lithium carbonate and the expanded graphite, and mechanically milling for 8-10 hours to prepare the lithium carbonate particles coated by the carbon nano particles.
6. A positive electrode sheet for a high-energy high-rate lithium battery, characterized in that the positive electrode sheet contains the positive electrode additive component according to any one of claims 1 to 4.
7. A preparation method of a high-energy high-rate lithium battery positive plate is characterized by comprising the following steps: the positive electrode additive as claimed in any one of claims 1 to 4, in a mass ratio of: conductive agent: the adhesive is 100: 0.1: 0.5-100: 1.5:2, mixing the materials in proportion, gradually diluting the mixture by using N-methyl pyrrolidone under stirring to obtain positive electrode slurry, and coating, drying at 90-100 ℃ and rolling the slurry to obtain the target positive electrode sheet.
8. The method for preparing the positive plate of the high-energy high-rate lithium battery as claimed in claim 7, wherein the mass of the positive electrode additive is 0.1-10% of the mass of the positive electrode active material, and the positive electrode active material is one or more of a lithium metal oxide with a layered structure, a lithium-free metal oxide, a lithium metal oxide with a spinel structure, a lithium metal phosphate, a lithium metal fluoride sulfate and a lithium metal vanadate.
9. The method according to claim 8, wherein the layered lithium metal oxide is selected from Lithium Cobaltate (LCO), nickel cobalt manganese ternary material (NCM), nickel cobalt aluminum ternary material (NCA); the lithium-free metal oxide is selected from V2O5Or MnO2(ii) a The spinel-structured lithium metal oxide is selected from lithium manganate (LiMn)2O4) (ii) a The lithium metal phosphate is selected from lithium iron phosphate (LFP); the lithium metal fluorinated sulfate is selected from the group consisting of fluorinated lithium cobalt sulfate (LiCoFSO)4) (ii) a The lithium metal vanadate is selected from nickel lithium vanadate (LiNiVO)4)。
10. The method for preparing the positive plate of the high-energy high-rate lithium battery as claimed in claim 7, wherein the conductive agent is one or more of graphite, acetylene black, conductive carbon black, superconducting carbon black, graphene, carbon nanotubes, conductive fibers, metal powder and organic conductive polymers; the graphite is selected from natural graphite or artificial graphite; the acetylene black is selected from Ketjen black; the conductive fibers are selected from carbon fibers or metal fibers; the metal powder is selected from copper powder or nickel powder; the organic conductive polymer is selected from polyphenylene derivatives; the adhesive is one or more of polyvinylidene fluoride, polyvinyl alcohol, polyurethane, polyacrylate, butyl rubber, epoxy resin, vinyl acetate resin and chlorinated rubber.
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Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120315550A1 (en) * | 2009-12-11 | 2012-12-13 | Ningbo Institute Of Materials Technology And Engineering, Chinese Academy Of Sciences | Graphene-modified lithium iron phosphate positive electrode active material, preparation of the same and lithium-ion secondary cell |
| JP2014035859A (en) * | 2012-08-08 | 2014-02-24 | Toyota Motor Corp | Positive electrode active material composite material and use of the same |
| CN104577130A (en) * | 2014-12-13 | 2015-04-29 | 山东神工海特电子科技有限公司 | Flexible-packaged high-power lithium iron phosphate power battery |
| CN106784997A (en) * | 2017-01-19 | 2017-05-31 | 西安瑟福能源科技有限公司 | A kind of emergency starting ultra-high magnification lithium ion battery |
| CN107785578A (en) * | 2016-08-25 | 2018-03-09 | 宁德时代新能源科技股份有限公司 | Positive electrode additive, preparation method thereof, positive plate and lithium ion secondary battery |
| CN107910538A (en) * | 2017-11-27 | 2018-04-13 | 中南大学 | Graphene/carbon coats lithium manganese phosphate vanadium phosphate cathode material and preparation method |
| CN108390041A (en) * | 2018-02-28 | 2018-08-10 | 石河子大学 | Foamed nickel current collector LiFePO4/graphene composite material electrode slice and preparation method thereof |
| CN108428867A (en) * | 2018-03-09 | 2018-08-21 | 深圳市溢骏科技有限公司 | Fast charging type lithium ion battery and preparation method thereof |
| CN108649220A (en) * | 2018-04-24 | 2018-10-12 | 芜湖浙鑫新能源有限公司 | Carbon-coated nickelic lithium ion battery anode glue size and preparation method thereof |
| WO2019034105A1 (en) * | 2017-08-18 | 2019-02-21 | 宁波致良新能源有限公司 | Positive electrode material and preparation method thereof, positive electrode and lithium ion battery |
| CN109417162A (en) * | 2018-09-28 | 2019-03-01 | 宁波致良新能源有限公司 | Anode additive and preparation method thereof, anode and preparation method thereof and lithium ion battery |
| CN109802094A (en) * | 2017-11-15 | 2019-05-24 | 成都特隆美储能技术有限公司 | A kind of low temperature ferric phosphate lithium cell and preparation method thereof |
| US20190267663A1 (en) * | 2018-02-23 | 2019-08-29 | Nanotek Instruments, Inc. | Method of Producing Elastomer Composite-Encapsulated Particles of Anode Active Materials for Lithium Batteries |
| US20190267662A1 (en) * | 2018-02-23 | 2019-08-29 | Nanotek Instruments, Inc. | Elastomer Composite-Encapsulated Particles of Anode Active Materials for Lithium Batteries |
| CN110797530A (en) * | 2019-09-26 | 2020-02-14 | 惠州锂威新能源科技有限公司 | High-voltage lithium cobalt oxide graphite battery and preparation method thereof |
| CN110911644A (en) * | 2019-10-30 | 2020-03-24 | 深圳市卓能新能源股份有限公司 | Lithium ion positive coating and lithium ion battery |
| CN111213260A (en) * | 2017-08-17 | 2020-05-29 | 微宏动力系统（湖州）有限公司 | Anode, anode preparation method and lithium ion battery |
| CN111599984A (en) * | 2019-02-21 | 2020-08-28 | 贝特瑞新材料集团股份有限公司 | Positive plate, lithium ion battery comprising positive plate and preparation method of lithium ion battery |
-
2020
- 2020-09-10 CN CN202010946715.1A patent/CN112054202A/en active Pending
Patent Citations (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120315550A1 (en) * | 2009-12-11 | 2012-12-13 | Ningbo Institute Of Materials Technology And Engineering, Chinese Academy Of Sciences | Graphene-modified lithium iron phosphate positive electrode active material, preparation of the same and lithium-ion secondary cell |
| JP2014035859A (en) * | 2012-08-08 | 2014-02-24 | Toyota Motor Corp | Positive electrode active material composite material and use of the same |
| CN104577130A (en) * | 2014-12-13 | 2015-04-29 | 山东神工海特电子科技有限公司 | Flexible-packaged high-power lithium iron phosphate power battery |
| CN107785578A (en) * | 2016-08-25 | 2018-03-09 | 宁德时代新能源科技股份有限公司 | Positive electrode additive, preparation method thereof, positive plate and lithium ion secondary battery |
| CN106784997A (en) * | 2017-01-19 | 2017-05-31 | 西安瑟福能源科技有限公司 | A kind of emergency starting ultra-high magnification lithium ion battery |
| CN111213260A (en) * | 2017-08-17 | 2020-05-29 | 微宏动力系统（湖州）有限公司 | Anode, anode preparation method and lithium ion battery |
| CN109874306A (en) * | 2017-08-18 | 2019-06-11 | 宁波致良新能源有限公司 | Positive electrode and preparation method thereof, anode and lithium ion battery |
| WO2019034105A1 (en) * | 2017-08-18 | 2019-02-21 | 宁波致良新能源有限公司 | Positive electrode material and preparation method thereof, positive electrode and lithium ion battery |
| CN109802094A (en) * | 2017-11-15 | 2019-05-24 | 成都特隆美储能技术有限公司 | A kind of low temperature ferric phosphate lithium cell and preparation method thereof |
| CN107910538A (en) * | 2017-11-27 | 2018-04-13 | 中南大学 | Graphene/carbon coats lithium manganese phosphate vanadium phosphate cathode material and preparation method |
| US20190267663A1 (en) * | 2018-02-23 | 2019-08-29 | Nanotek Instruments, Inc. | Method of Producing Elastomer Composite-Encapsulated Particles of Anode Active Materials for Lithium Batteries |
| US20190267662A1 (en) * | 2018-02-23 | 2019-08-29 | Nanotek Instruments, Inc. | Elastomer Composite-Encapsulated Particles of Anode Active Materials for Lithium Batteries |
| CN108390041A (en) * | 2018-02-28 | 2018-08-10 | 石河子大学 | Foamed nickel current collector LiFePO4/graphene composite material electrode slice and preparation method thereof |
| CN108428867A (en) * | 2018-03-09 | 2018-08-21 | 深圳市溢骏科技有限公司 | Fast charging type lithium ion battery and preparation method thereof |
| CN108649220A (en) * | 2018-04-24 | 2018-10-12 | 芜湖浙鑫新能源有限公司 | Carbon-coated nickelic lithium ion battery anode glue size and preparation method thereof |
| CN109417162A (en) * | 2018-09-28 | 2019-03-01 | 宁波致良新能源有限公司 | Anode additive and preparation method thereof, anode and preparation method thereof and lithium ion battery |
| CN111599984A (en) * | 2019-02-21 | 2020-08-28 | 贝特瑞新材料集团股份有限公司 | Positive plate, lithium ion battery comprising positive plate and preparation method of lithium ion battery |
| CN110797530A (en) * | 2019-09-26 | 2020-02-14 | 惠州锂威新能源科技有限公司 | High-voltage lithium cobalt oxide graphite battery and preparation method thereof |
| CN110911644A (en) * | 2019-10-30 | 2020-03-24 | 深圳市卓能新能源股份有限公司 | Lithium ion positive coating and lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| LEWANDOWSKI,A ETAL.: "Properties of the lithium and graphite-lithium anodes in N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide", JOURNAL OF POWER SOURCES, vol. 197, no. 1, pages 502 - 507, XP026446372 * |
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