CN109616601A - A kind of prelithiation film of high lithium content and its preparation method and application - Google Patents
A kind of prelithiation film of high lithium content and its preparation method and application Download PDFInfo
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- CN109616601A CN109616601A CN201811005890.XA CN201811005890A CN109616601A CN 109616601 A CN109616601 A CN 109616601A CN 201811005890 A CN201811005890 A CN 201811005890A CN 109616601 A CN109616601 A CN 109616601A
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
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Abstract
The invention discloses prelithiation films of a kind of high lithium content and its preparation method and application, comprising: the prelithiation layer of the basement membrane of 1um-50um and the 0.02um-100um being coated on the basement membrane；Prelithiation layer includes: the second prelithiation material of the first prelithiation material of 1wt%-99wt%, 1wt%-99wt%, the binder of 0.01wt%-10wt%, the conductive additive of 0%-10wt%, the dispersing agent of 0wt%-2wt% and the auxiliary agent of 0wt%-2wt%；Wherein, the mass ratio of the first prelithiation material and the second prelithiation material is 5-100；The granularity of first prelithiation material is between 500nm-5um, and the granularity of the second prelithiation material is between 50nm-500nm；First prelithiation material and the second prelithiation material are respectively as follows: can occur the material that electrochemical reaction releases lithium ion under voltage control.
Description
Technical field
The present invention relates to the prelithiation films and its preparation side of lithium battery material technical field more particularly to a kind of high lithium content
Method and application.
Background technique
Output voltage is high, energy density is high, have extended cycle life, have a safety feature, memoryless effect because having for lithium ion battery
The features such as answering is successfully applied to mobile power source field as main energy storage device.For further satisfaction power grid energy storage, electronic
The demand of automobile and consumer electronics product to energy storage device, more long circulation life, safety is more preferable, energy density is higher
Electrode material and lithium battery system become research hotspot.
During the work time, lithium ion shuttles lithium battery in positive and negative anodes.The height of lithium battery energy density is very big
In a part depend on battery in active lithium-ion number.However at present in the lithium battery in commercialization, anode material when first all
Material and negative electrode material often irreversible consumption lithium ion.Therefore it supplements the lithium ion being consumed and effectively improves lithium electricity as one kind
The means of pond energy density.
Prelithiation technology is mainly cathode prelithiation, positive prelithiation etc. at present, and cathode prelithiation often uses lithium metal
Or the stronger lithiated materials of reproducibility compare environmental requirement during making and using and extremely endanger as lithium source
Danger.And lithiated materials are often directly coated with positive electrode by positive prelithiation together, reduce positive electrode use
Amount, therefore reduce the reversible capacity of battery.
However, existing prelithiation technology, often the attainable prelithiation amount of institute is smaller, and therefore, there is an urgent need to propose one
The prelithiation membrane technology of kind high lithium content reaches the requirement for improving full battery capacity to realize biggish prelithiation amount.
Summary of the invention
The present invention provides prelithiation films of a kind of high lithium content and its preparation method and application.High lithium content of the invention
Prelithiation film include that basement membrane, the first prelithiation material for being coated on its surface, the second prelithiation material, binder, conduction add
Add agent, dispersing agent and auxiliary agent；Using the battery of material of the present invention in first all operational process, the prelithiation film of high lithium content discharges
Lithium ion out, for supplementing the loss of first all electrode material lithium ions, the prelithiation film of high lithium content has both ceramic diaphragm simultaneously
The advantages of, improve the performances such as use temperature, the absorbency of diaphragm.The preparation method letter of the prelithiation film of high lithium content of the present invention
Single, abundant raw materials low to environmental requirement, simple process, are easy to be mass produced；High lithium content provided by the present invention it is pre-
Lithiumation film can be applied in liquid lithium ionic cell, quasi- solid lithium ion battery, all-solid-state battery and lithium metal battery, energy
Enough have the function that effectively improve full battery capacity.
In a first aspect, the embodiment of the invention provides a kind of prelithiation films of high lithium content, comprising: the basement membrane of 1um-50um
With the prelithiation layer for the 0.02um-100um being coated on the basement membrane；
The prelithiation layer includes: the second pre- lithium of the first prelithiation material of 1wt%-99wt%, 1wt%-99wt%
Change material, the binder of 0.01wt%-10wt%, the conductive additive of 0%-10wt%, the dispersing agent of 0wt%-2wt% and
The auxiliary agent of 0wt%-2wt%；
Wherein, the mass ratio of the first prelithiation material and the second prelithiation material is 5-100；First prelithiation material
Granularity is between 500nm-5um, and the granularity of the second prelithiation material is between 50nm-500nm；
The first prelithiation material and the second prelithiation material, which are respectively as follows:, can occur electrification under voltage control
Learn the material that reaction releases lithium ion
Preferably, the first prelithiation material specifically includes: LixCuyOz、LixFeyOz、LixAlyOz、LixVyOz、
LixCoyOz、LixMnyOz、LixNiyOz、LixMgyOz、Li2(CuaNibMnc)O2, one of or a variety of combinations；
The second prelithiation material specifically includes: LixCyOz、Li2S、LixCuyOz、LixFeyOz、LixAlyOz、
LixVyOz、LixCoyOz、LixMnyOz、LixNiyOz、Li2C2O4、LixMgyOz、LixTiyOz、Li2(CuaNibMnc)O2One of
Or a variety of combination；
Wherein, x, y, z are integer or non-integer and the electricity price balance for meeting chemical formula；A+b+c=1, and 0 < a, b, c < 1.
Preferably, the basement membrane include polypropylene PP film, polythene PE film, nonwoven cloth diaphragm, fibre diaphragm, ceramics every
One of film, solid electrolyte diaphragm are a variety of compound.
Preferably, the prelithiation material is the particle of spherical, elliposoidal or random polygon.
Preferably, the binder is Kynoar, butadiene-styrene latex, styrene-acrylic latex, polyvinyl alcohol, ethyl vinyl acetate second
Alkene, sodium alginate, polyacrylamide, polymethyl methacrylate-butyl acrylate, ethylene-vinyl acetate copolymer, poly-vinegar acid
Vinyl acetate, polyurethane, hydroxyethyl cellulose, methyl hydroxyethylcellulose, sodium carboxymethylcellulose, polyacrylamide, polyoxygenated
The mixing of one or more of ethylene and polytetrafluoroethylene (PTFE)；
The conductive additive is carbon black, electrically conductive graphite, carbon fiber, carbon nanotube, acetylene black, section's qin carbon, graphene, gold
Belong to one or more kinds of mixing of silver, metallic gold, vapor-grown carbon fibers VGCF, electrically conductive graphite KS-6, carbon black SUPER-P；
The dispersing agent is Sodium Polyacrylate, neopelex, lauryl sodium sulfate, calgon, gathers
Acrylic acid, cetyl trimethylammonium bromide, polyethylene glycol, polyacrylic acid potassium, octylphenolpolyoxyethylene or sulfonate fluorine point
One or more of powder；
The auxiliary agent is dimethyl silicone polymer, silicone oil, polyethers, Sodium Polyacrylate, polyvinyl alcohol, alkyl polyoxyethylene
Ether carboxylic acid sodium, polyoxyethylated alkyl phenol, sodium alkyl benzene sulfonate, alkyl phenol polyoxyethylene ether, polyoxyethylene alkyl amine or polyoxy
The one or more combination of ethernamine.
Second aspect is used to prepare the pre- of high lithium content described in above-mentioned first aspect the embodiment of the invention provides a kind of
The preparation method of lithiumation film, comprising:
Dispersing agent, binder, conductive additive, auxiliary agent and solvent are added in pre- agitator tank in required ratio, dissolved
The first mixture is obtained completely；Wherein, the solvent be polar solvent, including deionized water, N-Methyl pyrrolidone NMP,
Alcohol or dimethylformamide DMF；The binder is Kynoar, butadiene-styrene latex, styrene-acrylic latex, polyvinyl alcohol, ethylene-
Vinyl acetate, sodium alginate, polyacrylamide, polymethyl methacrylate-butyl acrylate, ethylene-vinyl acetate copolymer,
Polyvinyl acetate, polyurethane, hydroxyethyl cellulose, methyl hydroxyethylcellulose, sodium carboxymethylcellulose, polyacrylamide,
The mixing of one or more of polyethylene glycol oxide and polytetrafluoroethylene (PTFE)；The conductive additive is carbon black, electrically conductive graphite, carbon
Fiber, carbon nanotube, acetylene black, section's qin carbon, graphene, metallic silver, metallic gold, one kind of VGCF, KS-6, SUPER-P or
A variety of mixing；The dispersing agent is Sodium Polyacrylate, neopelex, lauryl sodium sulfate, calgon, gathers
Acrylic acid, cetyl trimethylammonium bromide, polyethylene glycol, polyacrylic acid potassium, octylphenolpolyoxyethylene or sulfonate fluorine point
One or more of powder；The auxiliary agent is dimethyl silicone polymer, silicone oil, polyethers, Sodium Polyacrylate, polyethylene
Alcohol, Alkyl ethoxy carboxylate acid sodium, polyoxyethylated alkyl phenol, sodium alkyl benzene sulfonate, alkyl phenol polyoxyethylene ether, polyoxy second
The one or more combination of allylic alkylation amine or polyoxyethylate amide；
The second prelithiation material is added step-wise in first mixture in required ratio, dispersion is stirred, stirs
Mixing speed is 10-5000rpm, obtains the second mixture；Wherein the second prelithiation material specially can under voltage control
The material that electrochemical reaction releases lithium ion occurs；The granularity of second prelithiation material is between 50nm-500nm；
The first prelithiation material is added step-wise in second mixture in required ratio, dispersion is stirred, stirs
Mixing speed is 10-5000rpm, obtains third mixture；Wherein the first prelithiation material specially can under voltage control
The material that electrochemical reaction releases lithium ion occurs；The granularity of the first prelithiation material is between 500nm-5um；The
The mass ratio of one prelithiation material and the second prelithiation material is 5-100；
The third mixture is obtained into coating slurry with the screen to filtrate；
The coating slurry is coated on to one side or the two sides of basement membrane with the speed of 1m/min-100m/min, 40 DEG C-
The prelithiation film of high lithium content is obtained after drying at 100 DEG C；Wherein, the basement membrane includes PP film, PE film, non-woven membrane or fiber
Any one of film.
Preferably, it is described by the coating slurry with the speed of 1m/min-100m/min be coated on basement membrane one side or
Before two sides, the method also includes:
Sided corona treatment is carried out to the basement membrane.
Preferably, the method also includes: roll-in is carried out to the prelithiation film, roll temperature is at 10 DEG C -80 DEG C, roll-in
Pressure is in 0.4-0.7Mpa, and rate is in 1m/s-50m/s.
The third aspect, the embodiment of the invention provides a kind of progress of the prelithiation film of high lithium content described in first aspect
The method of prelithiation processing, comprising:
Lithium battery is assembled using the prelithiation film of the high lithium content as diaphragm material, wherein is coated with prelithiation layer
Side assembled close to anode pole piece；
The lithium battery that assembly obtains is subjected to charging chemical conversion；
Wherein, the lithium battery is divided according to structure composition, including liquid lithium battery, quasi- solid state lithium battery, solid-state lithium electricity
The one or more in pond；
Alternatively, the lithium battery is divided according to contour structures, including cylindrical lithium battery, quadrate lithium battery, soft package lithium battery,
The one or more of lamination lithium battery, button lithium battery.
Fourth aspect, the embodiment of the invention provides a kind of prelithiation including high lithium content described in above-mentioned first aspect
The lithium battery of film.
The prelithiation film of high lithium content of the invention includes basement membrane, the first prelithiation material for being coated on its surface, second
Prelithiation material, binder, conductive additive, dispersing agent and auxiliary agent；；Using the battery of material of the present invention in first all operational process
In, the prelithiation film of high lithium content releases lithium ion, for supplementing the loss of first all electrode material lithium ions, high lithium content
The advantages of prelithiation film has both ceramic diaphragm simultaneously improves the performances such as use temperature, the absorbency of diaphragm.The present invention is high, and lithium contains
The preparation method of the prelithiation film of amount is simple, abundant raw materials low to environmental requirement, simple process, is easy to be mass produced；This
The prelithiation film of high lithium content provided by inventing can be applied to liquid lithium ionic cell, quasi- solid lithium ion battery, Quan Gu
In state battery and lithium metal battery, it can have the function that effectively improve full battery capacity.
Detailed description of the invention
Below by drawings and examples, the technical solution of the embodiment of the present invention is described in further detail.
Fig. 1 is the structural schematic diagram of the prelithiation film of high lithium content provided in an embodiment of the present invention；
Fig. 2 is the preparation method flow chart of the prelithiation film of high lithium content provided in an embodiment of the present invention；
Fig. 3 is the prelithiation film SEM figure for the high lithium content that the embodiment of the present invention 1 provides；
Fig. 4 is the prelithiation film half-cell performance test figure for the high lithium content that the embodiment of the present invention 1 provides；
Fig. 5 is the partial enlarged view of Fig. 4.
Specific embodiment
Below with reference to embodiment, the present invention is further described in detail, but is not intended to limit guarantor of the invention
Protect range.
A kind of prelithiation film the embodiment of the invention provides high lithium content includes: the basement membrane of 1um-50um and is coated on base
The prelithiation layer of 0.02um-100um on film；Structure is as shown in Figure 1.
Prelithiation layer includes: the second prelithiation material of the first prelithiation material of 1wt%-99wt%, 1wt%-99wt%
Material, the binder of 0.01wt%-10wt%, the conductive additive of 0%-10wt%, the dispersing agent and 0wt%- of 0wt%-2wt%
The auxiliary agent of 2wt%；
Wherein, the mass ratio of the first prelithiation material and the second prelithiation material be 5-100, preferably 10-50 it
Between, particularly preferably between 10 and 20.The granularity of first prelithiation material is between 500nm-5um, the grain of the second prelithiation material
Degree is between 50nm-500nm.
Wherein, the first prelithiation material and the second prelithiation material, which are respectively as follows:, can occur electricity under voltage control
Chemical reaction releases the material of lithium ion.
Specifically, the first prelithiation material specifically includes: LixCuyOz、LixFeyOz、LixAlyOz、LixVyOz、LixCoyOz、
LixMnyOz、LixNiyOz、LixMgyOz、Li2(CuaNibMnc)O2, one of or a variety of combinations；
Second prelithiation material specifically includes: Li2S、LixCuyOz、LixFeyOz、LixAlyOz、LixVyOz、LixCoyOz、
LixMnyOz、LixNiyOz、Li2C2O4、LixMgyOz、LixTiyOz、LixCuy(PO4)z、LixFey(PO4)z、LixAly(PO4)z、
LixVy(PO4)z、LixMny(PO4)z、LixNiy(PO4)z、LixMgy(PO4)zOr LixTiy(PO4)zOne of or a variety of groups
It closes.
Above-mentioned first prelithiation material and the second prelithiation material after charging chemical conversion, be converted into material containing lithium source or
Without lithium source material.
Basement membrane includes polypropylene (PP) film, polyethylene (PE) film, nonwoven cloth diaphragm, fibre diaphragm, ceramic diaphragm, solid-state electricity
Solve one of matter diaphragm or a variety of compound.
Prelithiation material is the particle of spherical, elliposoidal or random polygon, it is preferred to use spheric granules.
Binder be Kynoar, butadiene-styrene latex, styrene-acrylic latex, polyvinyl alcohol, ethene-vinyl acetate, sodium alginate,
Polyacrylamide, polymethyl methacrylate-butyl acrylate, ethylene-vinyl acetate copolymer, polyvinyl acetate, poly- ammonia
Ester, hydroxyethyl cellulose, methyl hydroxyethylcellulose, sodium carboxymethylcellulose, polyacrylamide, polyethylene glycol oxide and poly- four
The mixing of one or more of vinyl fluoride；
Conductive additive is carbon black, electrically conductive graphite, carbon fiber, carbon nanotube, acetylene black, section's qin carbon, graphene, metal
Silver, metallic gold, vapor-grown carbon fibers (Vapor-grown carbon fiber, VGCF), electrically conductive graphite KS-6, carbon black
One or more kinds of mixing of SUPER-P；
Dispersing agent is Sodium Polyacrylate, neopelex, lauryl sodium sulfate, calgon, polypropylene
Acid, cetyl trimethylammonium bromide, polyethylene glycol, polyacrylic acid potassium, octylphenolpolyoxyethylene or sulfonate fluorine dispersing agent
One or more of；
Auxiliary agent is dimethyl silicone polymer, silicone oil, polyethers, Sodium Polyacrylate, polyvinyl alcohol, alkyl polyoxyethylene ether carboxylic
Sour sodium, polyoxyethylated alkyl phenol, sodium alkyl benzene sulfonate, alkyl phenol polyoxyethylene ether, polyoxyethylene alkyl amine or polyoxyethylene
The one or more combination of amide.
The prelithiation film of high lithium content of the invention includes basement membrane, the first prelithiation material for being coated on its surface, second
Prelithiation material, binder, conductive additive, dispersing agent and auxiliary agent；；Using the battery of material of the present invention in first all operational process
In, the prelithiation film of high lithium content releases lithium ion, for supplementing the loss of first all electrode material lithium ions, high lithium content
The advantages of prelithiation film has both ceramic diaphragm simultaneously improves the performances such as use temperature, the absorbency of diaphragm.The present invention is high, and lithium contains
The preparation method of the prelithiation film of amount is simple, abundant raw materials low to environmental requirement, simple process, is easy to be mass produced；This
The prelithiation film of high lithium content provided by inventing can be applied to liquid lithium ionic cell, quasi- solid lithium ion battery, Quan Gu
In state battery and lithium metal battery, it can have the function that effectively improve full battery capacity.
The preparation method of the prelithiation film of high lithium content provided in an embodiment of the present invention is introduced below.
The preparation method of the prelithiation film of high lithium content provided in this embodiment, step are as shown in Figure 2, comprising:
Step 210, dispersing agent, binder, conductive additive, auxiliary agent and solvent are added to pre- agitator tank in required ratio
In, dissolution obtains the first mixture completely；
Solvent is polar solvent, including deionized water, N-Methyl pyrrolidone NMP, alcohol or dimethylformamide DMF；
Binder is Kynoar, butadiene-styrene latex, styrene-acrylic latex, polyvinyl alcohol, ethene-vinyl acetate, sodium alginate, polyacrylamide
Amine, polymethyl methacrylate-butyl acrylate, ethylene-vinyl acetate copolymer, polyvinyl acetate, polyurethane, ethoxy
In cellulose, methyl hydroxyethylcellulose, sodium carboxymethylcellulose, polyacrylamide, polyethylene glycol oxide and polytetrafluoroethylene (PTFE)
One or more kinds of mixing；Conductive additive is carbon black, electrically conductive graphite, carbon fiber, carbon nanotube, acetylene black, section's qin carbon, stone
One or more kinds of mixing of black alkene, metallic silver, metallic gold, VGCF, KS-6, SUPER-P；Dispersing agent is water soluble dispersing agent,
It include: Sodium Polyacrylate, neopelex, lauryl sodium sulfate, calgon, polyacrylic acid, cetyl
One of trimethylammonium bromide, polyethylene glycol, polyacrylic acid potassium, octylphenolpolyoxyethylene or sulfonate fluorine dispersing agent or
It is a variety of；Auxiliary agent is dimethyl silicone polymer, silicone oil, polyethers, Sodium Polyacrylate, polyvinyl alcohol, Alkyl ethoxy carboxylate acid
Sodium, polyoxyethylated alkyl phenol, sodium alkyl benzene sulfonate, alkyl phenol polyoxyethylene ether, polyoxyethylene alkyl amine or polyoxyethylene acyl
The one or more combination of amine
Step 220, the second prelithiation material is added step-wise in first mixture in required ratio, is stirred
Dispersion, mixing speed 10-5000rpm obtain the second mixture；
Wherein, the second prelithiation material is specially and electrochemical reaction can occur under voltage control to release lithium ion
Material；It can specifically include:
LixCyOz、Li2S、LixCuyOz、LixFeyOz、LixAlyOz、LixVyOz、LixCoyOz、LixMnyOz、LixNiyOz、
Li2C2O4、LixMgyOz、LixTiyOz、Li2(CuaNibMnc)O2One of or a variety of combinations；
Wherein, x, y, z are integer or non-integer and the electricity price balance for meeting chemical formula；A+b+c=1, and 0 < a, b, c < 1.
Step 230, the first prelithiation material is added step-wise in second mixture in required ratio, is stirred
Dispersion, mixing speed 10-5000rpm obtain third mixture；
Wherein, the first prelithiation material is specially and electrochemical reaction can occur under voltage control to release lithium ion
Material specifically includes: LixCuyOz、LixFeyOz、LixAlyOz、LixVyOz、LixCoyOz、LixMnyOz、LixNiyOz、LixMgyOz、
Li2(CuaNibMnc)O2, wherein x, y, z are integer or non-integer and the electricity price balance for meeting chemical formula；A+b+c=1, and 0 < a,
b,c<1。
Step 240, third mixture is obtained into coating slurry with the screen to filtrate；
Step 250, coating slurry is coated on to one side or the two sides of basement membrane with the speed of 1m/min-100m/min,
The prelithiation film of high lithium content is obtained after drying at 40 DEG C -100 DEG C.
Wherein, basement membrane includes any one of PP film, PE film, non-woven membrane or tunica fibrosa.
Preferably, sided corona treatment can also be carried out to basement membrane before this step.
After this step, roll-in can also be carried out to prelithiation film, at 10 DEG C -80 DEG C, rolling pressure exists roll temperature
0.4-0.7Mpa, rate is in 1m/s-50m/s.
The preparation method of the prelithiation film of high lithium content of the present invention is simple, abundant raw materials low to environmental requirement, technique are simple
It is single, it is easy to be mass produced.
The prelithiation film of high lithium content of the invention is assembled into battery and carries out prelithiation processing, by the pre- of high lithium content
Lithiumation film assembles lithium battery as diaphragm material, wherein is assembled close to anode pole piece the side for being coated with prelithiation layer；
Then the lithium battery that assembly obtains is subjected to charging chemical conversion.
The lithium battery of assembly is divided according to structure composition, including liquid lithium battery, quasi- solid state lithium battery, solid state lithium battery
It is one or more kinds of；
Alternatively, being divided according to contour structures, including cylindrical lithium battery, quadrate lithium battery, soft package lithium battery, lamination lithium electricity
Pond, button lithium battery one or more.
Using the battery of material of the present invention in first all operational process, the prelithiation film of high lithium content releases lithium ion,
For supplementing the loss of first all electrode material lithium ion, the advantages of prelithiation film of high lithium content has both ceramic diaphragm simultaneously, mention
The performances such as high the use temperature of diaphragm, absorbency.
Below by specific example, technical solution of the present invention is further elaborated.
Embodiment 1
The prelithiation film for present embodiments providing a kind of high lithium content is starched including basement membrane and the lithiumation for being coated on basement membrane side
Expect the prelithiation layer constituted, wherein basement membrane is polypropylene porous film, with a thickness of 16um, using one side coating mode, coating thickness
In 2um, prelithiation layer is formed.Coating sizing-agent is according to mass ratio are as follows: lithiumation composition 20%, NMP 80%；Wherein, lithiumation combines
The preparation of object is according to mass ratio are as follows: the first lithiated materials Li2CuO2Powder is 70%, and partial size D50 is 1um, the second prelithiation material
Li2CuO2Powder is 10%, and partial size is that D50 is 200nm, and binder PVDF is 20%.
The prelithiation film of high lithium content in the present embodiment is prepared with the following method, specifically includes step:
(1) binder PVDF and deionized water are added in pre- agitator tank according to aforementioned proportion, dissolution completely, is mixed
Close object I；
(2) the second prelithiation material is added step-wise in mixture I, carries out high-speed stirred dispersion, speed of agitator is
50rpm disperses revolving speed 1700rpm, obtains mixture II；
(3) by the first prelithiation material Li2CuO2Powder is added step-wise in mixture II, is carried out high-speed stirred dispersion, is stirred
Mixing revolving speed is 50rpm, disperses revolving speed 1700rpm, obtains mixtures III；；
(4) coating slurry is obtained by filtration with 400 mesh screens in said mixture III；
(5) by the coating point of above-mentioned coating slurry in the one side of the basement membrane Jing Guo sided corona treatment, coating speed 5m/min,
50 DEG C of dryings obtain the prelithiation film of high lithium content after dry.
The SEM for the prelithiation film that the embodiment of the present invention 1 provides schemes as shown in figure 3, from figure 3, it can be seen that lithiated materials
It is evenly distributed.
By prelithiation film that the embodiment of the present invention 1 provides be coated with the anode pole piece of lithium cobaltate cathode material, be coated with
Cathode pole piece, the electrolyte of graphite dress up half-cell, and carry out battery performance test, as a result see Fig. 4.
Embodiment 2
The prelithiation film for present embodiments providing a kind of high lithium content is starched including basement membrane and the lithiumation for being coated on basement membrane side
Expect the prelithiation layer constituted, wherein basement membrane is polypropylene porous film, with a thickness of 16um, using one side coating mode, coating thickness
In 10um, prelithiation layer is formed.Coating sizing-agent is according to mass ratio are as follows: lithiumation composition 20%, NMP 80%；Wherein, lithiumation group
The preparation of object is closed according to mass ratio are as follows: the first lithiated materials Li2Cu0.95Ni0.05O2Powder is 50%, partial size D50 be 1um, second
Prelithiation material Li2Cu02Powder is 30%, partial size 100nm, and binder PVDF is 20%.
The method of the prelithiation film of high lithium content is prepared with embodiment 1.
Embodiment 3
The prelithiation film for present embodiments providing a kind of high lithium content is starched including basement membrane and the lithiumation for being coated on basement membrane side
Expect the prelithiation layer constituted, wherein basement membrane is polypropylene porous film, with a thickness of 16um, using one side coating mode, coating thickness
In 10um, prelithiation layer is formed.Coating sizing-agent is according to mass ratio are as follows: lithiumation composition 20%, NMP 80%；Wherein, lithiumation group
The preparation of object is closed according to mass ratio are as follows: the first prelithiation material Li2Cu0.5Ni0.5O2Powder is 20%, the second prelithiation material
Li2Cu0.5Ni0.5O2Powder is 20%, and partial size D50 is 1um, and alumina powder 10%, partial size D50 is 200nm binder PVDF
It is 50%.
The method of the prelithiation film of high lithium content is prepared with embodiment 1.
Comparative example 1
This comparative example provides a kind of prelithiation film, constitutes including basement membrane with the lithiumation slurry for being coated on basement membrane side
Prelithiation layer, wherein basement membrane is polypropylene porous film, and with a thickness of 16um, using one side coating mode, coating thickness is in 10um, shape
At prelithiation layer.Coating sizing-agent is according to mass ratio are as follows: lithiumation composition 20%, NMP 80%；Wherein, the preparation of lithiumation composition
According to mass ratio are as follows: lithiated materials Li2CuO2Powder is 80%, and partial size D50 is 1um, and binder PVDF is 20%.
The method of prelithiation film is prepared with embodiment 1.
The prelithiation film that comparative example 1 is provided and anode pole piece, lithium metal, the electrolyte for being coated with lithium cobaltate cathode material
Half-cell is dressed up, and carries out battery performance test, as a result sees Fig. 4 and Fig. 5, wherein Fig. 5 is the partial enlargement for irising out part in Fig. 4
Figure.
Comparative example 2
By ceramic Al2O3Diaphragm dresses up half electricity with anode pole piece, lithium metal, the electrolyte for being coated with lithium cobaltate cathode material
Pond, and battery performance test is carried out, as a result see Fig. 4 and Fig. 5.
Above-described specific embodiment has carried out further the purpose of the present invention, technical scheme and beneficial effects
It is described in detail, it should be understood that being not intended to limit the present invention the foregoing is merely a specific embodiment of the invention
Protection scope, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of prelithiation film of high lithium content, which is characterized in that the prelithiation film of the high lithium content includes: 1um-50um's
The prelithiation layer of basement membrane and the 0.02um-100um being coated on the basement membrane；
The prelithiation layer includes: the second prelithiation material of the first prelithiation material of 1wt%-99wt%, 1wt%-99wt%
Material, the binder of 0.01wt%-10wt%, the conductive additive of 0%-10wt%, the dispersing agent and 0wt%- of 0wt%-2wt%
The auxiliary agent of 2wt%；
Wherein, the mass ratio of the first prelithiation material and the second prelithiation material is 5-100；The granularity of first prelithiation material
Between 500nm-5um, the granularity of the second prelithiation material is between 1nm-500nm；
The first prelithiation material and the second prelithiation material are respectively as follows: under voltage control that electrochemistry can to occur anti-
The material of lithium ion should be released.
2. the prelithiation film of high lithium content according to claim 1, which is characterized in that the first prelithiation material is specific
It include: LixCuyOz、LixFeyOz、LixAlyOz、LixVyOz、LixCoyOz、LixMnyOz、LixNiyOz、LixMgyOz、Li2
(CuaNibMnc)O2, one of or a variety of combinations；
The second prelithiation material specifically includes: LixCyOz、Li2S、LixCuyOz、LixFeyOz、LixAlyOz、LixVyOz、
LixCoyOz、LixMnyOz、LixNiyOz、Li2C2O4、LixMgyOz、LixTiyOz、Li2(CuaNibMnc)O2One of or it is a variety of
Combination；
Wherein, x, y, z are integer or non-integer and the electricity price balance for meeting chemical formula；A+b+c=1, and 0 < a, b, c < 1.
3. the prelithiation film of high lithium content according to claim 1, which is characterized in that the basement membrane includes polypropylene PP
One of film, polythene PE film, nonwoven cloth diaphragm, fibre diaphragm, ceramic diaphragm, solid electrolyte diaphragm are a variety of compound.
4. the prelithiation film of high lithium content according to claim 1, which is characterized in that the prelithiation material be it is spherical,
The particle of elliposoidal or random polygon.
5. the prelithiation film of high lithium content according to claim 1, which is characterized in that
The binder be Kynoar, butadiene-styrene latex, styrene-acrylic latex, polyvinyl alcohol, ethene-vinyl acetate, sodium alginate,
Polyacrylamide, polymethyl methacrylate-butyl acrylate, ethylene-vinyl acetate copolymer, polyvinyl acetate, poly- ammonia
Ester, hydroxyethyl cellulose, methyl hydroxyethylcellulose, sodium carboxymethylcellulose, polyacrylamide, polyethylene glycol oxide and poly- four
The mixing of one or more of vinyl fluoride；
The conductive additive is carbon black, electrically conductive graphite, carbon fiber, carbon nanotube, acetylene black, section's qin carbon, graphene, metal
One or more kinds of mixing of silver, metallic gold, vapor-grown carbon fibers VGCF, electrically conductive graphite KS-6, carbon black SUPER-P；
The dispersing agent is Sodium Polyacrylate, neopelex, lauryl sodium sulfate, calgon, polypropylene
Acid, cetyl trimethylammonium bromide, polyethylene glycol, polyacrylic acid potassium, octylphenolpolyoxyethylene or sulfonate fluorine dispersing agent
One or more of；
The auxiliary agent is dimethyl silicone polymer, silicone oil, polyethers, Sodium Polyacrylate, polyvinyl alcohol, alkyl polyoxyethylene ether carboxylic
Sour sodium, polyoxyethylated alkyl phenol, sodium alkyl benzene sulfonate, alkyl phenol polyoxyethylene ether, polyoxyethylene alkyl amine or polyoxyethylene
The one or more combination of amide.
6. a kind of preparation method for the prelithiation film for preparing any high lithium content of the claims 1-5, feature exist
In the preparation method includes:
Dispersing agent, binder, conductive additive, auxiliary agent and solvent are added in pre- agitator tank in required ratio, dissolution is complete
Obtain the first mixture；Wherein, the solvent be polar solvent, including deionized water, N-Methyl pyrrolidone NMP, alcohol or
Dimethylformamide DMF；The binder is Kynoar, butadiene-styrene latex, styrene-acrylic latex, polyvinyl alcohol, ethyl vinyl acetate second
Alkene, sodium alginate, polyacrylamide, polymethyl methacrylate-butyl acrylate, ethylene-vinyl acetate copolymer, poly-vinegar acid
Vinyl acetate, polyurethane, hydroxyethyl cellulose, methyl hydroxyethylcellulose, sodium carboxymethylcellulose, polyacrylamide, polyoxygenated
The mixing of one or more of ethylene and polytetrafluoroethylene (PTFE)；The conductive additive be carbon black, electrically conductive graphite, carbon fiber,
Carbon nanotube, acetylene black, section's qin carbon, graphene, metallic silver, metallic gold, the one or more of VGCF, KS-6, SUPER-P are mixed
It closes；The dispersing agent is Sodium Polyacrylate, neopelex, lauryl sodium sulfate, calgon, polypropylene
Acid, cetyl trimethylammonium bromide, polyethylene glycol, polyacrylic acid potassium, octylphenolpolyoxyethylene or sulfonate fluorine dispersing agent
One or more of；The auxiliary agent is dimethyl silicone polymer, silicone oil, polyethers, Sodium Polyacrylate, polyvinyl alcohol, alkane
Base polyoxyethylene ether carboxylic acid sodium, polyoxyethylated alkyl phenol, sodium alkyl benzene sulfonate, alkyl phenol polyoxyethylene ether, polyoxyethylene alkane
The one or more combination of base amine or polyoxyethylate amide；
The second prelithiation material is added step-wise in first mixture in required ratio, is stirred dispersion, stirring speed
Degree is 10-5000rpm, obtains the second mixture；Wherein the second prelithiation material is specially that can send out under voltage control
Raw electrochemical reaction releases the material of lithium ion；The granularity of second prelithiation material is between 50nm-500nm；
The first prelithiation material is added step-wise in second mixture in required ratio, is stirred dispersion, stirring speed
Degree is 10-5000rpm, obtains third mixture；Wherein the first prelithiation material is specially that can send out under voltage control
Raw electrochemical reaction releases the material of lithium ion；The granularity of the first prelithiation material is between 500nm-5um；First is pre-
Lithiated materials and the mass ratio of the second prelithiation material are 5-100；
The third mixture is obtained into coating slurry with the screen to filtrate；
The coating slurry is coated on to one side or the two sides of basement membrane with the speed of 1m/min-100m/min, at 40 DEG C -100
The prelithiation film of high lithium content is obtained after drying at DEG C；Wherein, the basement membrane includes PP film, PE film, non-woven membrane or tunica fibrosa
Any one of.
7. preparation method according to claim 6, which is characterized in that it is described by the coating slurry with 1m/min-100m/
The speed of min is coated on before one side or the two sides of basement membrane, the method also includes:
Sided corona treatment is carried out to the basement membrane.
8. preparation method according to claim 6, which is characterized in that the method also includes:
Roll-in is carried out to the prelithiation film, roll temperature is at 10 DEG C -80 DEG C, and rolling pressure is in 0.4-0.7Mpa, and rate is in 1m/
s-50m/s。
9. the method that the prelithiation film of any high lithium content of a kind of couple of the claims 1-5 carries out prelithiation processing,
It is characterized in that, which comprises
Lithium battery is assembled using the prelithiation film of the high lithium content as diaphragm material, wherein is coated with the one of prelithiation layer
It is assembled close to anode pole piece side；
The lithium battery that assembly obtains is subjected to charging chemical conversion；
Wherein, the lithium battery is divided according to structure composition, including liquid lithium battery, quasi- solid state lithium battery, solid state lithium battery
It is one or more kinds of；
Alternatively, the lithium battery is divided according to contour structures, including cylindrical lithium battery, quadrate lithium battery, soft package lithium battery, lamination
The one or more of lithium battery, button lithium battery.
10. a kind of lithium battery of the prelithiation film including any high lithium content of the claims 1-5.
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