CN109546081A - A kind of blended anode pole piece and preparation method thereof, lithium ion battery - Google Patents
A kind of blended anode pole piece and preparation method thereof, lithium ion battery Download PDFInfo
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- CN109546081A CN109546081A CN201811336167.XA CN201811336167A CN109546081A CN 109546081 A CN109546081 A CN 109546081A CN 201811336167 A CN201811336167 A CN 201811336167A CN 109546081 A CN109546081 A CN 109546081A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- 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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Abstract
The invention discloses a kind of blended anode pole pieces and preparation method thereof, lithium ion battery, the blended anode pole piece, including positive active material, binder and conductive agent, positive active material includes NCM811 single crystal grain and NCM811 second particle, wherein, the mass ratio of NCM811 single crystal grain and NCM811 second particle is (1:9)~(9:1)；A kind of preparation method of blended anode pole piece, comprising the following steps: 1) positive active material, binder, conductive agent and solvent are mixed and stirred evenly, form anode sizing agent；2) anode sizing agent is coated on plus plate current-collecting body aluminium foil, obtains blended anode pole piece after baking removal solvent.It is an advantage of the invention that having complementary advantages between NCM811 single crystal grain and NCM811 second particle due to including NCM811 single crystal grain and NCM811 second particle in positive active material, cycle performance of lithium ion battery and high-temperature storage performance are improved.
Description
Technical field
The present invention relates to field of lithium ion battery, more particularly to a kind of blended anode pole piece and preparation method thereof, lithium from
Sub- battery.
Background technique
With the development of new energy, high-energy density has become current trend, in order to meet the requirement of high-energy density,
Positive electrode gradually develops to NCM811 from NCM111, NCM523, NCM622, and NCM811 material is according to the particle shape of material
It is divided into single crystal grain and two kinds of second particle with composition, and respectively there are advantage and disadvantage between the two.
For NCM811 second particle, it has higher gram volume, but its security performance is poor, and high temperature follows
Ring and high-temperature storage performance are poor, the poor processability of NCM811 second particle, require processing environment high.
For NCM811 single crystal grain, relative to NCM811 second particle, it has a lower gram volume, but it
Security performance it is more preferable.NCM811 second particle has better chemical property, but poor processability, thermal stability is poor,
Poor safety performance, and there is preferable processing performance and preferable thermal stability and preferable safety for NCM811 single crystal grain
Performance, but chemical property is poor, the two performance is just opposite.
At present in conventional anode pole piece, individual NCM811 single crystal grain or NCM811 single crystal grain are generally used, is made
It obtains anode pole piece obtained and all there is certain performance deficiency, limit the use scope of lithium ion battery.
Summary of the invention
Goal of the invention: in view of the above-mentioned problems, an object of the present invention is to provide a kind of blended anode pole piece, to solve just
Pole pole piece there is technical issues that certain.
The second object of the present invention is to provide a kind of preparation method of blended anode pole piece.
The third object of the present invention is to provide a kind of lithium ion battery.
Technical solution:
A kind of blended anode pole piece, including positive active material, binder and conductive agent, positive active material include
NCM811 single crystal grain and NCM811 second particle, wherein the mass ratio of NCM811 single crystal grain and NCM811 second particle is
(1:9)~(9:1).Due to including NCM811 single crystal grain and NCM811 second particle in positive active material, it can make up for it that
This shortcomings that, plays advantage preferably, wherein second particle have better chemical property, but security performance and
Thermal stability is poor, and single crystal grain and second particle have opposite characteristic, has preferable safety and stability, but electric
Chemical property is poor, only needs preferably to mix by predetermined ratio between the two, does not need the change for carrying out special process, directly presses
Prior art can be met the requirements, and the two is mixed will perfectly play the advantages of the two, and makes up mutual deficiency, and
Have complementary advantages between NCM811 single crystal grain and NCM811 second particle, can be improved lithium that blended anode pole piece is prepared from
The cycle performance and high-temperature storage performance of sub- battery.
The mass percent of positive active material is 90~99% in one of the embodiments, the quality hundred of conductive agent
Dividing than the mass percent for 0.5~8.0%, adhesive is 0.5~2.0%.
Binder is Kynoar in one of the embodiments, and conductive agent is combined conductive agent.
A kind of preparation method of blended anode pole piece, comprising the following steps:
1) positive active material, binder, conductive agent and solvent are mixed and is stirred evenly, form anode sizing agent；
2) anode sizing agent is coated on plus plate current-collecting body aluminium foil, blended anode pole can be obtained after baking removal solvent
Piece；
Wherein, positive active material includes NCM811 single crystal grain and NCM811 second particle, wherein NCM811 monocrystalline
The mass ratio of grain and NCM811 second particle is (1:9)~(9:1).Due to positive active material include NCM811 single crystal grain and
NCM811 second particle mixes with other compositions and obtains anode sizing agent after stirring evenly, and obtains blended anode pole piece, energy after coating baking
Enough it is uniformly mixed NCM811 single crystal grain and NCM811 second particle, the blended anode pole piece structure made is stablized.
The mass percent of positive active material is 90~99% in one of the embodiments, the quality hundred of conductive agent
Dividing than the mass percent for 0.5~8.0%, adhesive is 0.5~2.0%.
Solvent is N-Methyl pyrrolidone in one of the embodiments, and the additional amount of solvent is anode sizing agent gross mass
20~27%.
A kind of lithium ion battery, including cathode pole piece and the blended anode pole piece.Due to including blended anode pole piece,
The cycle performance of lithium ion battery and high-temperature storage performance made is improved significantly.
The utility model has the advantages that compared with prior art, the invention has the advantages that
1) above-mentioned blended anode pole piece, due to including NCM811 single crystal grain and NCM811 bis- times in positive active material
Grain, the shortcomings that can make up for it each other, plays advantage preferably, between NCM811 single crystal grain and NCM811 second particle
There are synergistic effects, can be improved the cycle performance and high-temperature storage characteristics of the lithium ion battery that blended anode pole piece is prepared
Energy.
2) preparation method of above-mentioned blended anode pole piece, due to positive active material include NCM811 single crystal grain and
NCM811 second particle mixes with other compositions and obtains anode sizing agent after stirring evenly, and obtains blended anode pole piece, energy after coating baking
Enough it is uniformly mixed NCM811 single crystal grain and NCM811 second particle, the blended anode pole piece structure made is stablized.
3) above-mentioned lithium ion battery, due to including blended anode pole piece, the cycle performance of lithium ion battery and height made
Warm storge quality is improved significantly.
Detailed description of the invention
Fig. 1 is the embodiment of the present invention 1~3 and the cycle life of lithium ion battery contrast curve chart that comparative example 1,2 obtains；
Fig. 2 is the scanning electron microscope (SEM) photograph of NCM811 single crystal grain of the invention；
Fig. 3 is the scanning electron microscope (SEM) photograph of NCM811 second particle of the invention；
Fig. 4 is the scanning electron microscope (SEM) photograph of the blended anode pole piece of embodiment 1；
Fig. 5 is the XRD diagram of NCM811 single crystal grain of the invention, NCM811 second particle；
Fig. 6 be NCM811 single crystal grain of the invention, NCM811 second particle 003 peak XRD comparison diagram；
Fig. 7 be NCM811 single crystal grain of the invention, NCM811 second particle 104 peaks XRD comparison diagram.
Specific embodiment
Embodiment 1
A kind of blended anode pole piece, including positive active material, binder and conductive agent, positive active material include
NCM811 single crystal grain and NCM811 second particle, wherein the mass ratio of NCM811 single crystal grain and NCM811 second particle is
(1:9)~(9:1).Wherein, the mass percent of positive active material is 90~99%, and the mass percent of conductive agent is 0.5
~8.0%, the mass percent of adhesive is 0.5~2.0%.
Preferably, binder is Kynoar, and conductive agent is combined conductive agent, and combined conductive agent is specially conductive black
With the mixture of conductive carbon nanotube, wherein the mass ratio of conductive black and conductive carbon nanotube is 1:2.
Please refer to figs. 2 and 3, and Fig. 2 is the SEM figure under NCM811 single crystal grain × 30000 enlargement ratios.
Fig. 3 is the SEM figure under NCM811 second particle × 30000 enlargement ratios.
Wherein, the XRD of NCM811 single crystal grain and NCM811 second particle is as shown in Fig. 5~7.
A kind of lithium ion battery, including battery core, shell, battery core is by above-mentioned blended anode pole piece and cathode pole piece and membrane coil
Around forming.
The preparation method of above-mentioned lithium ion battery, comprising the following steps:
The preparation of S100, blended anode pole piece.
The preparation method of blended anode pole piece, specifically includes the following steps:
1) positive active material, binder, conductive agent and solvent are mixed and is stirred evenly, form anode sizing agent；
2) anode sizing agent is coated on plus plate current-collecting body aluminium foil, obtains blended anode pole piece after baking removal solvent；
Wherein, positive active material includes NCM811 single crystal grain and NCM811 second particle, wherein NCM811 monocrystalline
The mass ratio of grain and NCM811 second particle is (1:9)~(9:1).Wherein, the SEM figure such as Fig. 4 of the blended anode pole piece obtained
It is shown.
In the present embodiment, the mass percent that positive active material accounts for blended anode pole piece is 97.8%, wherein NCM monocrystalline
The mass ratio of particle and NCM811 second particle is 4:6, binder PVDF5130, and binder accounts for the quality of blended anode pole piece
Percentage is 1.0%, and the mass percent that conductive agent accounts for blended anode pole piece is 1.2%, and solvent is N-Methyl pyrrolidone, molten
Additional amount of the agent in step 1) is the 27% of anode sizing agent total weight.
After S200, the blended anode pole piece for obtaining step S100 carry out roll-in, cutting, brush dust, wound with cathode pole piece
Core is made, after core hot pressing, soldering polar ear, rubberizing, aluminum plastic film encapsulation, vacuum bakeout, carries out fluid injection and room temperature is stood
48h, to get battery core, battery core will be put into shell, and inject electrolyte to get lithium after battery core chemical conversion, degasification, sealing, partial volume
Ion battery.
Embodiment 2
The present embodiment and the distinctive points of embodiment 1 are: in the present embodiment, NCM single crystal grain and NCM811 second particle
Mass ratio be 8:2.
Embodiment 3
The present embodiment and the distinctive points of embodiment 1 are: in the present embodiment, NCM single crystal grain and NCM811 second particle
Mass ratio be 2:8.
Embodiment 4
The present embodiment and the distinctive points of embodiment 1 are: in the present embodiment, NCM single crystal grain and NCM811 second particle
Mass ratio be 1:9.
Embodiment 5
The present embodiment and the distinctive points of embodiment 1 are: in the present embodiment, NCM single crystal grain and NCM811 second particle
Mass ratio be 9:1.
Comparative example 1
The distinctive points of this comparative example and embodiment 1 are: in this comparative example, positive active material only has NCM811 monocrystalline
Grain.
Comparative example 2
The distinctive points of this comparative example and embodiment 1 are: in this comparative example, positive active material only has NCM811 bis- times
Grain.
Performance test
By lithium ion battery made from Examples 1 to 5 and comparative example 1,2, electric performance test, test result such as table 1 are carried out
And shown in Fig. 1.
Fig. 1 is that Examples 1 to 5 and comparative example 1,2 carry out the circulation that charge and discharge cycles obtain under the conditions of 45 DEG C, 1C/1C
Number-capacity retention ratio data graphs.
The lithium ion battery battery performance comparison result of 1 Examples 1 to 5 of table and comparative example 1~2
By Fig. 1 and table 1 it is found that the lithium ion battery that the embodiment of the present invention 1~5 obtains, gram volume is preferable, and high temperature holds
Amount conservation rate, high-temperature storage performance are preferable, and comprehensive performance is preferable.
The lithium ion battery of comparative example 1, only capacity retention ratio is higher, but gram volume is poor.
The lithium ion battery of comparative example 2, gram volume is higher, but high-temperature storage performance and high temperature capacity retention ratio are poor,
Mainly as the cycle progresses, the primary particle between second particle generates crack, and new crack and electrolyte reaction generate
By-product causes performance of lithium ion battery to reduce.
The lithium ion battery that the embodiment of the present invention 1~5 obtains, due to mono- containing NCM811 simultaneously in blended anode pole piece
Brilliant particle and NCM811 second particle, two kinds of ingredients cooperate, and have synergistic effect, have complementary advantages, can make lithium-ion electric
The comprehensive performance in pond is optimal state.
Claims (7)
1. a kind of blended anode pole piece, which is characterized in that including positive active material, binder and conductive agent, positive electrode active material
Matter includes NCM811 single crystal grain and NCM811 second particle, wherein the matter of NCM811 single crystal grain and NCM811 second particle
Amount is than being (1:9)~(9:1).
2. a kind of blended anode pole piece according to claim 1, which is characterized in that the mass percent of positive active material
It is 90~99%, the mass percent of conductive agent is 0.5~8.0%, the mass percent of adhesive is 0.5~2.0%.
3. a kind of blended anode pole piece according to claim 1, which is characterized in that binder is Kynoar, conductive
Agent is combined conductive agent.
4. a kind of preparation method of blended anode pole piece according to claim 1, which comprises the following steps:
1) positive active material, binder, conductive agent and solvent are mixed and is stirred evenly, form anode sizing agent；
2) anode sizing agent is coated on plus plate current-collecting body aluminium foil, blended anode pole piece can be obtained after baking removal solvent；
Wherein, positive active material includes NCM811 single crystal grain and NCM811 second particle, wherein NCM811 single crystal grain and
The mass ratio of NCM811 second particle is (1:9)~(9:1).
5. a kind of preparation method of blended anode pole piece according to claim 4, which is characterized in that positive active material
Mass percent is 90~99%, the mass percent of conductive agent is 0.5~8.0%, the mass percent of adhesive be 0.5~
2.0%.
6. a kind of preparation method of blended anode pole piece according to claim 4, which is characterized in that solvent is N- methyl pyrrole
Pyrrolidone, the additional amount of solvent are the 20~27% of anode sizing agent gross mass.
7. a kind of lithium ion battery, which is characterized in that including mixing described in cathode pole piece and claims 1 to 3 any one
Anode pole piece.
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| CN201811336167.XA CN109546081A (en) | 2018-11-12 | 2018-11-12 | A kind of blended anode pole piece and preparation method thereof, lithium ion battery |
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| CN201811336167.XA CN109546081A (en) | 2018-11-12 | 2018-11-12 | A kind of blended anode pole piece and preparation method thereof, lithium ion battery |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111640912A (en) * | 2020-05-13 | 2020-09-08 | 力神动力电池系统有限公司 | Positive pole piece, preparation method thereof and lithium ion secondary battery |
| CN111952590A (en) * | 2020-07-08 | 2020-11-17 | 河南科隆新能源股份有限公司 | Lithium ion battery positive electrode material for improving safety and cycle performance and preparation method thereof |
| CN114342119A (en) * | 2019-08-30 | 2022-04-12 | 住友金属矿山株式会社 | Positive electrode active material for lithium ion secondary battery and lithium ion secondary battery |
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| CN102169990A (en) * | 2011-04-07 | 2011-08-31 | 先进储能材料国家工程研究中心有限责任公司 | Ternary cathode material and production method thereof |
| CN103811744A (en) * | 2014-02-13 | 2014-05-21 | 北大先行科技产业有限公司 | Method for preparing ternary positive electrode material of lithium ion battery |
| CN107681128A (en) * | 2017-08-14 | 2018-02-09 | 北大先行科技产业有限公司 | A kind of anode material for lithium-ion batteries and preparation method thereof |
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| CN102169990A (en) * | 2011-04-07 | 2011-08-31 | 先进储能材料国家工程研究中心有限责任公司 | Ternary cathode material and production method thereof |
| CN103811744A (en) * | 2014-02-13 | 2014-05-21 | 北大先行科技产业有限公司 | Method for preparing ternary positive electrode material of lithium ion battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114342119A (en) * | 2019-08-30 | 2022-04-12 | 住友金属矿山株式会社 | Positive electrode active material for lithium ion secondary battery and lithium ion secondary battery |
| EP4023605A4 (en) * | 2019-08-30 | 2023-09-27 | Sumitomo Metal Mining Co., Ltd. | Positive electrode active material for lithium ion secondary batteries, and lithium ion secondary battery |
| EP4023603A4 (en) * | 2019-08-30 | 2023-12-06 | Sumitomo Metal Mining Co., Ltd. | Positive electrode active material for lithium ion secondary battery, and lithium ion secondary battery |
| EP4023604A4 (en) * | 2019-08-30 | 2023-12-06 | Sumitomo Metal Mining Co., Ltd. | Positive electrode active material for lithium ion secondary batteries, and lithium ion secondary battery |
| CN111640912A (en) * | 2020-05-13 | 2020-09-08 | 力神动力电池系统有限公司 | Positive pole piece, preparation method thereof and lithium ion secondary battery |
| CN111952590A (en) * | 2020-07-08 | 2020-11-17 | 河南科隆新能源股份有限公司 | Lithium ion battery positive electrode material for improving safety and cycle performance and preparation method thereof |
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