CN109713229A - A kind of preparation method of anode pole piece and lithium ion battery comprising it - Google Patents
A kind of preparation method of anode pole piece and lithium ion battery comprising it Download PDFInfo
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- CN109713229A CN109713229A CN201910088686.7A CN201910088686A CN109713229A CN 109713229 A CN109713229 A CN 109713229A CN 201910088686 A CN201910088686 A CN 201910088686A CN 109713229 A CN109713229 A CN 109713229A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The present invention relates to a kind of preparation method of anode pole piece and include its lithium ion battery, anode pole piece includes rich lithium additive, anode material for lithium-ion batteries, conductive agent and binder, it is added together with conductive agent and binder into solvent after first rich lithium additive is sufficiently mixed with anode material for lithium-ion batteries, last film dries roll-in, the richness lithium additive contain can deintercalation go out the lithium-containing compound of lithium ion, lithium-containing compound can deintercalation go out more lithium ions, supplement cathode forms the Li of SEI film loss+, the first charge-discharge efficiency of lithium battery is improved, promotes the gram volume of battery, and then promote the charge-discharge performance and cycle life of lithium ion battery, and simple process, raw material sources are easy to get, production application value with higher.
Description
Technical field
The present invention relates to lithium ion battery preparation technical fields, and in particular to a kind of preparation method of anode pole piece and comprising
Its lithium ion battery.
Background technique
With the development of New Energy Industry, at present in field of batteries, lithium ion battery is as green, the new energy electricity of environmental protection
Pond has been increasingly appearing in people's lives.Lithium ion battery is high, small in size, light-weight with energy density, fills
The velocity of discharge is fast, does not have the advantages that memory effect.
With the fast development of global economy, the non-renewable energy resources such as fossil energy are constantly consumed, air pollution and the whole world
The environmental problems such as warm are got worse so that people to efficiently, cleaning, sustainable energy demand increasingly increase.But it can be again
The raw energy has to be converted by means of efficient energy and memory technology can just be effectively used.Lithium ion battery is with it
Operating voltage is high, energy density is big, charge discharge life is long, self discharge is small, memory-less effect and it is environmental-friendly outstanding advantages of, closely
It is had received widespread attention over year and becomes the hot spot of research.Currently, lithium ion battery has been widely used as small portable electronic
The power supply of equipment, future will be expected to large-scale application in every field, and alleviate the energy and environmental problem in the whole world.
Electrode material is one of the key factor for restricting performance of lithium ion battery, especially positive electrode, in lithium-ion electric
The specific gravity highest (about 30-40%) accounted in the cost structure of pond, it has also become the key of performance of lithium ion battery is further increased, it is existing
Have the anode material for lithium-ion batteries gram volume in technology lower, and the lithium ion that goes out of deintercalation when chemical conversion because want shape
A part is also consumed at solid electrolyte interface layer (Solid electrolyte interface, SEI), in charge and discharge
The Li of free state in the process+Also it ceaselessly can deposit and lose activity, seriously affect the charge-discharge performance of lithium ion battery
And cycle life.
Therefore, how a kind of anode slice of lithium ion battery that gram volume is high is provided and the lithium ion battery haveing excellent performance is
Those skilled in the art's urgent problem to be solved.
Summary of the invention
In view of this, the present invention provides the lithium ion battery that a kind of preparation method of anode pole piece includes it, the present invention
The battery of preparation has bigger specific energy and longer cycle life.
In order to achieve the above object, the present invention adopts the following technical scheme:
Firstly, the present invention provides a kind of preparation methods of lithium-rich anode pole piece, comprising the following steps:
(1) rich lithium additive granules are thoroughly mixed with anode active material of lithium ion battery, obtain dry powder blend
Object；
(2) mixture made from the step (1) and conductive agent, binder are sequentially added into solvent, mixes and stirs
It mixes uniformly, obtains mixed serum；
(3) mixed serum made from the step (2) is evenly applied in aluminum foil current collector, in 60-90 DEG C of condition
Lower drying, is dried to solvent and volatilizees completely, and wherein drying time is 20-80s；Roll-in is after the completion of drying to get anode pole piece.
The beneficial effect of above-mentioned technical proposal is: providing a kind of preparation method of anode pole piece, passes through rich lithium additive
The addition of particle, effectively increases the gram volume of positive electrode, simple process and easily operated.
Preferably, step (1) the rich lithium additive be for the first time can deintercalation go out the > rich lithium material of 200mAh/g lithium ion,
And partial size≤20 μm.
By adopting the above technical scheme the utility model has the advantages that the addition of the rich lithium additive of high deintercalation amount effectively increases positive material
The gram volume of material can extend the charge discharge life of battery, and partial size≤20 μm, convenient for rich lithium additive and positive-active material
The uniform mixing of remaining material such as material, conductive agent.
Preferably, richness lithium additive described in step (1) is stratiform richness lithium material xLi2MnO3·(1-x)LiMO2, Fu Li
Material Li1.17Ni0.25Mn0.58O2, rich lithium antifluorite structure Li5FeO4In any one or a few mixture, wherein
xLi2MnO3·(1-x)LiMO2In 0 < x < 1, any one in M Ni, Co, Mn, preferably rich lithium antifluorite structure
Li5FeO4。
By adopting the above technical scheme the utility model has the advantages that above-mentioned lithium-containing compound can deintercalation go out more Li+, participate in being formed
SEI layers (solid electrolyte interface layer), reduce Li in positive active material+Consumption, so as to guarantee to have more Li+
Insertion and abjection are participated in, thus lithium battery first charge-discharge efficiency can be improved and extend the charge and discharge cycles longevity of lithium battery
Life, and the Li of rich lithium antifluorite structure5FeO4It being capable of the Li of deintercalation out+At most, theoretical capacity can reach 700mAh/g, and stratiform is rich
Lithium material xLi2MnO3·(1-x)LiMO2With rich lithium material Li1.17Ni0.25Mn0.58O2, theoretical capacity 200-300mAh/g.
Further, richness lithium additive preferred embodiment described in step (1) is with Li5FeO4For primary raw material, and
Li5FeO4Quality Zhan always rich lithium additive quality 70% or more, with xLi2MnO3·(1-x)LiMO2With
Li1.17Ni0.25Mn0.58O2Supplemented by, and the two quality proportioning 1:1.
Preferably, anode active material of lithium ion battery described in step (1) is LiNixCoyMnzO2(x+y+z=1),
LiCoO2, Spinel LiMn2O4、LiFePO4In any one or several mixtures, wherein LiNixCoyMnzO2In x+
Y+z=1；
Further, anode active material of lithium ion battery described in step (1) is preferably LiFePO4。
By adopting the above technical scheme the utility model has the advantages that above-mentioned lithium-containing compound can deintercalation go out more Li+, and above just
Pole material is all the common materials that current mainstream technology uses, the mating convenience of consistent, technical maturity, production equipment.
Preferably, conductive agent described in step (2) is electrically conductive graphite, acetylene black, carbon nanotube, any one in graphene
Or several mixture；
Further, conductive agent preferred embodiment described in step (2) be based on carbon nanotube, the total conductive agent of quality Zhan
50% or more, electrically conductive graphite, acetylene black, supplemented by graphene, three's quality proportioning is 1:1:1.
By adopting the above technical scheme the utility model has the advantages that above-mentioned conductive agent is that current mainstream technology usually uses, technology is steady
Fixed, technical maturity, the mating convenience of production equipment.
Preferably, binder described in step (2) is polyvinylidene fluoride, one in polyvinylidene fluoride-perfluoropropene
Kind or two kinds of mixture；
Further, binder described in step (2) is preferably polyvinylidene fluoride and polyvinylidene fluoride-perfluoropropene
Mixture, the quality proportioning of the two are 1:1.
By adopting the above technical scheme the utility model has the advantages that being able to maintain chemical stability in the organic electrolyte of lithium battery；With
And electrochemical stability is kept in charge and discharge process；There is preferable caking property simultaneously and do not pollute, supply is convenient.
Preferably, solvent described in step (2) is N-Methyl pyrrolidone or deionized water.
By adopting the above technical scheme the utility model has the advantages that can dissolve above-mentioned binder and with all the components in above-mentioned formula
Chemical reaction is not generated；It is important that not polluting, facilitate recycling.
Preferably, the matter of the rich lithium additive, anode active material of lithium ion battery, conductive agent, binder and solvent
Amount is than being (1-15): 90:1:1:(80-100).
By adopting the above technical scheme the utility model has the advantages that anode active material of lithium ion battery, conductive agent, binder and solvent
The gram volume of positive electrode is promoted, and then promote lithium-ion electric by adulterating a certain proportion of rich lithium additive for optimal proportion
The cycle life in pond.
Preferably, solvent residual mass ratio≤0.001% after the completion of being dried described in step (3).
The present invention also provides a kind of lithium ion batteries, including anode pole piece described in above-mentioned technical proposal；Further include: it is negative
Pole pole piece, electrolyte and shell, charging voltage > 4.0V when the lithium ion battery is melted into, and the ratio of the lithium ion battery
Energy >=280Wh/kg, cycle life >=5000 time.
By using above-mentioned technical proposal, using high voltage when the present invention has following technical effect that chemical conversion, can make
Rich lithium additive deintercalation goes out more Li+, to effectively achieve the purpose that improve positive gram volume, extend battery life.
Preferably, the negative electrode active material of the cathode pole piece be graphite, it is hard carbon, carbonaceous mesophase spherules, any in silicon-carbon
One or more of mixtures；The electrolyte is organic electrolyte or polymer dielectric.
In conclusion compared with prior art, the present invention has following technical effect that rich by adulterating in positive electrode
Lithium additive, make positive electrode can deintercalation go out more lithium ions, promote the free lithium ion in positive gram volume and battery, make
The first charge-discharge efficiency of battery is increased to 95% from 90%, and battery specific energy promotes 7-15%, and battery cycle life extends 30-
50%, and preparation process easy easily manipulation, raw material sources are easy to get, production application value with higher.
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment 1
The embodiment of the present invention 1 provides a kind of preparation method of anode pole piece, comprising the following steps:
(1) rich lithium additive is thoroughly mixed with anode active material of lithium ion battery, obtains mixture；
(2) mixture made from the step (1) and conductive agent, binder are successively added into solvent step by step, are mixed
Merging stirs evenly, and obtains mixed serum；
(3) mixed serum made from the step (2) is evenly applied in aluminum foil current collector, 60-90 DEG C of drying 20-
80s, then roll-in is to get anode pole piece.
Wherein, the rich lithium additive in step (1) is stratiform richness lithium material xLi2MnO3·(1-x)LiMO2, rich lithium material
Li1.17Ni0.25Mn0.58O2Or the Li of rich lithium antifluorite structure5FeO4One of or a variety of mixtures, and partial size≤20 μm,
In, xLi2MnO3·(1-x)LiMO2In 0 < x < 1, one of M Ni, Co, Mn；Anode active material of lithium ion battery is
LiNixCoyMnzO2(x+y+z=1), LiCoO2, Spinel LiMn2O4Or LiFePO4One or more of mixture；
Conductive agent in step (2) is a variety of mixtures of one of electrically conductive graphite, acetylene black, carbon nanotube, graphene；
Binder is one of polyvinylidene fluoride, polyvinylidene fluoride-perfluoropropene or two kinds of mixture, and solvent is N- first
Base pyrrolidones or deionized water；
Meanwhile rich lithium additive, anode active material of lithium ion battery, conductive agent, binder and solvent mass ratio be
(1-15): 90:1:1:(80-100).
Embodiment 2-8
The preparation method for the positive agent piece that 2-8 of the embodiment of the present invention is provided according to above-described embodiment 1, the phase provided with table 1
Raw material and proportion is answered to be prepared for positive agent piece, specific raw material and proportion are as shown in table 1:
Table 1
Embodiment 9-15
Embodiment 9-15 provides a kind of lithium ion battery, wherein lithium based on anode pole piece prepared by embodiment 2-8
Cathode pole piece, electrolyte and the shell that ion battery includes are as shown in table 2；And to embodiment 9-15 provide lithium ion battery into
Go the test of battery specific energy and cycle life, as shown in the table:
Table 2
Each embodiment in this specification is described in a progressive manner, the highlights of each of the examples are with other
The difference of embodiment, the same or similar parts in each embodiment may refer to each other.For device disclosed in embodiment
For, since it is corresponded to the methods disclosed in the examples, so being described relatively simple, related place is said referring to method part
It is bright.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (10)
1. a kind of preparation method of anode pole piece, which comprises the following steps:
(1) rich lithium additive granules are thoroughly mixed with anode active material of lithium ion battery, obtain powder mixture；
(2) mixture made from the step (1) and conductive agent, binder are sequentially added into solvent, is mixed and stirred for
It is even, obtain mixed serum；
(3) mixed serum made from the step (2) is evenly applied in aluminum foil current collector, is dried under conditions of 60-90 DEG C
It is dry, it is dried to solvent and volatilizees completely, wherein drying time is 20-80s；Roll-in is after the completion of drying to get anode pole piece.
2. a kind of preparation method of anode pole piece according to claim 1, which is characterized in that step (1) the rich lithium adds
Add agent be for the first time can deintercalation go out the > rich lithium material of 200mAh/g lithium ion, and partial size≤20 μm.
3. a kind of preparation method of anode pole piece according to claim 2, which is characterized in that richness lithium described in step (1)
Additive is stratiform richness lithium material xLi2MnO3·(1-x)LiMO2, rich lithium material Li1.17Ni0.25Mn0.58O2, rich lithium antifluorite knot
The Li of structure5FeO4In any one or a few mixture, wherein xLi2MnO3·(1-x)LiMO2In 0 < x < 1, M Ni,
Any one in Co, Mn.
4. a kind of preparation method of anode pole piece according to claim 1, which is characterized in that lithium described in step (1) from
Sub- battery anode active material is LiNixCoyMnzO2(x+y+z=1), LiCoO2, Spinel LiMn2O4、LiFePO4In it is any
One or several kinds of mixtures, wherein LiNixCoyMnzO2In x+y+z=1.
5. a kind of preparation method of anode pole piece according to claim 1, which is characterized in that conduction described in step (2)
Agent is the mixture of electrically conductive graphite, acetylene black, carbon nanotube, any one or a few in graphene.
6. a kind of preparation method of anode pole piece according to claim 1, which is characterized in that bonded described in step (2)
Agent is the mixture of one or both of polyvinylidene fluoride, polyvinylidene fluoride-perfluoropropene.
7. a kind of preparation method of anode pole piece according to claim 1, which is characterized in that solvent described in step (2)
For N-Methyl pyrrolidone or deionized water.
8. a kind of preparation method of anode pole piece according to claim 1, which is characterized in that the richness lithium additive, lithium
Ion battery positive electrode active materials, conductive agent, binder and solvent mass ratio be (1-15): 90:1:1:(80-100).
9. a kind of lithium ion battery, which is characterized in that including such as described in any item anode pole pieces of claim 1-9；Further include:
Cathode pole piece, electrolyte and shell, charging voltage > 4.0V when the lithium ion battery is melted into, and the lithium ion battery
Specific energy >=280Wh/kg, cycle life >=5000 time.
10. a kind of lithium ion battery according to claim 9, which is characterized in that the negative electrode active material of the cathode pole piece
Expect for the mixture of any one or a few in graphite, hard carbon, carbonaceous mesophase spherules, silicon-carbon；The electrolyte is organic electrolysis
Liquid or polymer dielectric.
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| CN110320478A (en) * | 2019-06-19 | 2019-10-11 | 天津力神电池股份有限公司 | A method of detection negative electrode of lithium ion battery is to additive demand |
| CN112259721A (en) * | 2020-10-28 | 2021-01-22 | 湖北融通高科先进材料有限公司 | Lithium iron phosphate-lithium-rich oxide compound and preparation method thereof |
| CN113410447A (en) * | 2021-06-23 | 2021-09-17 | 万向一二三股份公司 | Positive electrode material and method for improving conductivity and cycle life of lithium ion battery |
| WO2021184220A1 (en) * | 2020-03-17 | 2021-09-23 | 温州玖源锂电池科技发展有限公司 | Lithium ion start-stop power supply capable of being pre-lithiated and preparation method therefor |
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| CN114597525A (en) * | 2022-03-22 | 2022-06-07 | 远景动力技术(江苏)有限公司 | Lithium ion battery and application thereof |
| CN114784223A (en) * | 2022-04-28 | 2022-07-22 | 广东马车动力科技有限公司 | Positive plate and preparation method and application thereof |
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| WO2021184220A1 (en) * | 2020-03-17 | 2021-09-23 | 温州玖源锂电池科技发展有限公司 | Lithium ion start-stop power supply capable of being pre-lithiated and preparation method therefor |
| CN112259721A (en) * | 2020-10-28 | 2021-01-22 | 湖北融通高科先进材料有限公司 | Lithium iron phosphate-lithium-rich oxide compound and preparation method thereof |
| CN114497460A (en) * | 2020-11-12 | 2022-05-13 | 荣盛盟固利新能源科技有限公司 | Lithium ion battery positive pole piece, preparation method and lithium ion battery |
| CN113471417A (en) * | 2021-05-28 | 2021-10-01 | 中国科学院宁波材料技术与工程研究所 | High-voltage positive electrode material composition and lithium ion battery |
| CN113410447B (en) * | 2021-06-23 | 2022-09-02 | 万向一二三股份公司 | Positive electrode material and method for improving conductivity and cycle life of lithium ion battery |
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| WO2023133820A1 (en) * | 2022-01-14 | 2023-07-20 | 宁德时代新能源科技股份有限公司 | Positive electrode plate and secondary battery comprising same |
| CN114597525A (en) * | 2022-03-22 | 2022-06-07 | 远景动力技术(江苏)有限公司 | Lithium ion battery and application thereof |
| CN114784223A (en) * | 2022-04-28 | 2022-07-22 | 广东马车动力科技有限公司 | Positive plate and preparation method and application thereof |
| WO2023225849A1 (en) * | 2022-05-24 | 2023-11-30 | 宁德新能源科技有限公司 | Electrochemical apparatus and electronic device |
| WO2023225857A1 (en) * | 2022-05-24 | 2023-11-30 | 宁德新能源科技有限公司 | Electrochemical apparatus and electronic device |
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Application publication date: 20190503 |