CN110137485A - A kind of preparation method of the silicium cathode material containing surface modification film - Google Patents
A kind of preparation method of the silicium cathode material containing surface modification film Download PDFInfo
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Abstract
A kind of preparation method of the silicium cathode material containing surface modification film, belongs to technical field of lithium ion.The method are as follows: polymer is dissolved into water, silicon materials are added, heat while stirring, removes the moisture in solution, obtains the silicon materials for being coated with polymer film A；PAN is dissolved in nmp solvent, stirring makes it completely dissolved, and the silicon materials for being coated with polymer film A and conductive agent are added in PAN solution, are heated while stirring, and removes the nmp solvent in solution, obtains the silicium cathode material containing surface modification film.The manually modified film of the silicium cathode of invention can satisfy the binder that common SBR class is used in silicon-carbon cathode, so that graphite and each self-generating of silicium cathode are suitble to the SEI film of oneself, without influencing each other, further promote the cyclical stability of battery.The manually modified membrane preparation method of silicium cathode of the present invention is simple and convenient, and can satisfy silicon-carbon cathode and use the method ingredient of conventional water system ingredient.
Description
Technical field
The invention belongs to technical field of lithium ion more particularly to a kind of silicium cathode materials containing surface modification film
Preparation method.
Background technique
It is a large amount of due to the higher energy density of lithium ion battery, longer cycle life and advantages of environment protection
It applies on the portable electronic products and new-energy automobile such as mobile phone, laptop, and traditional lithium using graphite as cathode
Ion battery energy density has arrived bottleneck, and energy density is difficult to break through.
In order to obtain the lithium ion battery of higher energy density, nano-silicon, the sub- silicon of oxidation and silicon-carbon enter lithium ion
The world of battery, however, the expansion pulverizing problem of silicium cathode cannot be solved at all with the problem of poor circulation, so,
Nano-silicon, silicon-carbon or the mixing material for aoxidizing sub- silicon and graphite are referred to as silicon-carbon cathode as negative electrode material, gradually by exploitation and
Using.But the mode of silicon and graphite in conjunction with lithium ion is different, silicon is alloying reaction, and graphite is deintercalation reaction, is applicable in
SEI film it is also different, lead to binder, the selection of electrolyte also can be different, these discrepancys make the viscous of silicon-carbon cathode
Knot agent and the selection of electrolyte are difficult to combine the applicability of graphite and silicium cathode, such as styrene butadiene rubber sbr class flexible
Binder is suitble to graphite cathode, but is difficult to inhibit the expansion of silicium cathode and be not suitable for；And rich in carboxylic hydroxyl, rigid polypropylene
Sour PAA class and carboxymethyl cellulose salt CMC class binder are suitable for silicium cathode, but too many and uncomfortable to graphite cathode side reaction
With.Therefore silicon-carbon cathode needs formed respectively on silicium cathode surface and graphite cathode surface using different binders it is different
SEI film.There are some patent literature reports SBR class and the application of PAA class, CMC class hybrid adhesive in silicon-carbon cathode at present,
Such as the application for a patent for invention of Publication No. CN105633411A proposes one kind using polyacrylic acid and Lithium polyacrylate as master bond
Agent, is cooperation binder with butadiene-styrene rubber, the compound binding agent suitable for silicon-carbon cathode；Authorization Notice No. is CN106058259B
The high-specific-capacity silicon carbon cathode compound binding agent that uses of patent of invention include 5~50wt% of sodium carboxymethylcellulose, polypropylene
20~90wt% of acid 5~30wt% and butadiene-styrene rubber.But either butadiene-styrene rubber class binder, polyacrylic binder, also
It is carboxymethyl cellulose salt class binder is all aqueous binders, simple mixing is difficult to play respectively negative to silicium cathode or graphite
The advantage of pole, in addition it is more obvious to the side effect of silicon-carbon cathode, influence cycle performance.
Higher energy density is the target that lithium ion battery is constantly challenged, to avoid simple high specific energy silicium cathode battery
Circulation expansion is big, the fast problem of capacity attenuation, and silicon carbide or the mixing material for aoxidizing sub- silicon and graphite, i.e. silicon-carbon cathode become
Feasible one of the strategy for promoting lithium ion battery energy density.But silicon and graphite cathode in charge and discharge process with lithium ion
Reaction is different, and the SEI film being applicable in is different, causes the selection of the chemical systems such as binder, electrolyte contradiction occur, the two is difficult
It is compatible.Single graphite mould binder is selected, the expansion for inhibiting silicon and the shape for being unfavorable for stable silicium cathode SEI film are unfavorable for
At；Single silicon type binder is selected, graphite cathode side reaction is more, and capacity is low, is unfavorable for stable graphite cathode SEI film
It is formed；And the binder for selecting the two compound, divide because two kinds of binders will not be according to graphite cathode particle and silicium cathode particle
Distribution is opened, effect instead can be worse.
Summary of the invention
The purpose of the present invention is to solve the cycle performance of high specific energy silicon-carbon cathode is unstable, binder is not applicable to be asked
Topic, provides a kind of preparation method of silicium cathode material containing surface modification film, by silicium cathode material prepared by the present invention and stone
Ink is used cooperatively, and collectively as negative electrode active material, the negative product of silicon-carbon is made, and polymer forms modified membrane on the negative product surface of silicon-carbon,
The energy density and cycle performance of the lithium ion battery using the silicon-carbon cathode can be improved.
To achieve the above object, the technical solution adopted by the present invention is as follows:
A kind of preparation method of the silicium cathode material containing surface modification film, the method comprises the following steps:
Step 1: polymer is dissolved into water, and the mass fraction of polymer is 0.1%~100%, and silicon material is added later
Material, heats while stirring at a temperature of 40~80 DEG C, removes the moisture in solution, or use spray drying process, removes moisture removal, obtain
The silicon materials of polymer film A must be coated with；The polymer is in polyacrylate, carboxymethyl cellulose salt and alginate
It is one or more of；
Step 2: PAN is dissolved in nmp solvent, and stirring makes it completely dissolved, and it is 0.1%~100% that mass fraction, which is made,
PAN solution；The silicon materials for being coated with polymer film A and conductive agent that step 1 obtains are added in PAN solution, in 40
It heats while stirring at a temperature of~120 DEG C, removes the nmp solvent in solution, or use spray drying process, remove nmp solvent, obtain
To the silicium cathode material containing surface modification film, the surface modification film is polymer film A and PAN microporous barrier.
A kind of lithium ion battery of the silicium cathode material containing above-mentioned preparation, the lithium ion battery are coiled lithium ion
Battery or stack type lithium ion battery；The lithium ion battery contains positive plate, negative electrode tab, isolation film, electrolyte or electrolyte,
The active material of the negative electrode tab is collectively constituted by silicium cathode material and graphite.
A kind of preparation method of the silicium cathode material containing surface modification film, the method comprises the following steps:
Step 1: polymer is dissolved into water, and the mass fraction of polymer is 0.1%~100%, and it is negative that silicon is added later
Pole heats while stirring at a temperature of 40~80 DEG C, removes the moisture in solution, or use spray drying process, removes moisture removal, obtain
The silicium cathode of polymer film A must be coated with；The polymer is in polyacrylate, carboxymethyl cellulose salt and alginate
It is one or more of；
Step 2: PEO is dissolved in THF solvent, and stirring makes it completely dissolved, and it is 0.1~100% that mass fraction, which is made,
PEO solution；The silicium cathode, conductive agent and lithium salts for being coated with polymer film A that step 1 is obtained are added in PEO solution, in
It heats while stirring at a temperature of 30~60 DEG C, removes the THF solvent in solution, or use spray drying process, remove THF solvent,
The silicium cathode material containing surface modification film is obtained, the surface modification film is polymer film A and PEO copolymer solid electrolyte
Film.
A kind of lithium ion battery of the silicium cathode material containing above-mentioned preparation, the lithium ion battery are coiled lithium ion
Battery or stack type lithium ion battery；The lithium ion battery contains positive plate, negative electrode tab, isolation film, electrolyte or electrolyte,
The active material of the negative electrode tab is made of silicium cathode material and graphite.
The present invention having the beneficial effect that compared with the existing technology
(1) the manually modified film silicium cathode material that the present invention is obtained using two step liquid phase methods or two step spray drying processes is in lithium
SEI film stable, suitable for silicium cathode, and PAN microporous barrier or PEO solid are capable of forming in ion battery charge and discharge process
Dielectric film can inhibit the expansion of silicium cathode, improve the long-term cycle stability of silicon-carbon cathode.
(2) the manually modified film of silicium cathode of the invention can satisfy the bonding that common SBR class is used in silicon-carbon cathode
Agent, without influencing each other, further promotes following for battery so that graphite and each self-generating of silicium cathode are suitble to the SEI film of oneself
Ring stability.
(3) the manually modified membrane preparation method of silicium cathode of the present invention is simple and convenient, and can satisfy silicon-carbon cathode and make
With the method ingredient of conventional water system ingredient.
Detailed description of the invention
Fig. 1 is the preparation method process and mechanism figure of the silicium cathode containing surface modification film；
Fig. 2 is different manually modified film silicon-carbon batteries and unmodified battery under the conditions of 45 DEG C of 2.5V-4.2V 1C/1C
Loop-around data figure；
Fig. 3 is different manually modified film silicon-carbon batteries and unmodified battery under the conditions of 45 DEG C of 2.5V-4.2V 1C/1C
Circulation expansion plans.
Specific embodiment
Further description of the technical solution of the present invention with reference to the accompanying drawings and examples, and however, it is not limited to this,
All to be modified to technical solution of the present invention or equivalent replacement, range without departing from the spirit of the technical scheme of the invention should all
Cover within the protection scope of the present invention.
As shown in Figure 1, the present invention uses PAA-Li or CMC-Li etc. as the manually modified inner membrance A of silicium cathode material, to mix
There is PAN microporous barrier or PEO- lithium salts solid electrolyte layer of conductive agent etc. to be used as the manually modified outer membrane B of silicium cathode material, inner membrance A
Excellent silicium cathode SEI film is formed, outer membrane B possesses good lithium ion and electronic conductivity, can reduce impedance, flexible
PAN microporous barrier or PEO solid electrolyte film can inhibit the expansion of silicium cathode, while outer membrane B also can prevent aqueous solution to inner membrance A
Destruction so that the production of silicon-carbon cathode diaphragm can be using conventional water system dosing method, while binder can select graphite normal
The SBR class binder of rule.
The present invention contains the silicium cathode of surface modification film, it is contemplated that the unique SEI film of silicon-carbon cathode, lithium ion and electronics electricity
Special use environment needed for conductance and silicon-carbon cathode ingredient has larger difference with traditional silicon and the direct simple mixing ingredient of graphite
Different, made silicon-carbon cathode diaphragm has lower electrode polarization, the excellent distribution of SEI film and the expansion of lower circulating battery
Rate, these greatly improve the cyclical stability of silicon-carbon cathode.
The present invention coats one layer of nanoscale, on silicium cathode surface conducive to the polymer film A of silicium cathode SEI film growth, example
Such as Lithium polyacrylate PAA-Li, then coat the polymer film B of one layer of hydrophobic porous conduction, such as polyacrylonitrile (PAN) film.Polymer
The effect of film B is to keep apart the SBR class binder suitable for graphite and the polymer film A suitable for silicon.In this way, modify it
When silicon materials (such as nano-silicon, the sub- silicon of oxidation or silicon carbide) afterwards mix composition silicon-carbon cathode with graphite, used bonding
The SBR class binder that agent can be selected merely conducive to graphite, the presence of polymer film A and B can inhibit the swollen of silicium cathode
It is swollen, it is formed, while excessive side reaction will not be generated to graphite cathode, is also beneficial to steady conducive to stable silicium cathode SEI film
Fixed graphite cathode SEI film is formed.The cyclical stability of high specific energy silicon-carbon cathode battery is effectively improved, battery is improved
Cycle life.It is modified by the early period to silicon carbide or the sub- silicium cathode particle of oxidation, forms a surface modification be applicable in, stable
Film is to solve one of the most effective strategy of silicon-carbon cathode binder applicability in space structure level, for promoting high specific energy silicon
Cycle performance, the battery life of Carbon anode battery have most direct influence.
Specific embodiment 1: present embodiment record be a kind of silicium cathode material containing surface modification film preparation
Method, the method comprises the following steps:
Step 1: polymer is dissolved into water, and the mass fraction of polymer is 0.1%~100%, and silicon material is added later
Material, heats while stirring at a temperature of 40~80 DEG C, removes the moisture in solution, or use spray drying process, removes moisture removal, obtain
The silicon materials of the polymer film A of nanometer grade thickness must be coated with；The polymer be polyacrylate, carboxymethyl cellulose salt and
One or more of alginate；
Step 2: PAN (polyacrylonitrile) is dissolved in NMP (N-Methyl pyrrolidone) solvent, and stirring makes it completely dissolved,
The PAN solution that mass fraction is 0.1%~100% is made；Silicon materials for being coated with polymer film A that step 1 is obtained and
Conductive agent is added in PAN solution, is heated while stirring at a temperature of 40~120 DEG C, removes the nmp solvent in solution, or adopt
With spray drying process, nmp solvent is removed, obtains the silicium cathode material containing surface modification film, the surface modification film is polymerization
Object film A and PAN microporous barrier.The conductive agent is carbons conductive agent, and the carbons conductive agent is acetylene black, conducting polymer, carbon
One of nanotube, graphene or multiple combinations.
Specific embodiment 2: a kind of system of the silicium cathode material containing surface modification film described in specific embodiment one
Preparation Method, in step 1, the polyacrylate is one of polyacrylic acid, Lithium polyacrylate or Sodium Polyacrylate；It is described
Carboxymethyl cellulose salt is sodium carboxymethylcellulose or carboxymethyl cellulose lithium；The alginate is sodium alginate or alginic acid
Lithium.
Specific embodiment 3: a kind of system of the silicium cathode material containing surface modification film described in specific embodiment one
Preparation Method, in step 1, the mass fraction of the polymer/silicon materials is 2.0%~100%；The silicon materials be nano-silicon,
Silicon carbide aoxidizes sub- silicon.
Specific embodiment 4: a kind of system of the silicium cathode material containing surface modification film described in specific embodiment one
Preparation Method, in step 2, the PAN/ is coated with silicon materials=0.5wt%~99wt% of polymer film A；The conductive agent
Content is 0.1wt%~8wt%.
Specific embodiment 5: a kind of silicium cathode containing any specific embodiment preparation of specific embodiment one to four
The lithium ion battery of material, the lithium ion battery are coiled lithium ion battery or stack type lithium ion battery；The lithium from
Sub- battery contains positive plate, negative electrode tab, isolation film, electrolyte or electrolyte, and the active material of the negative electrode tab is by silicium cathode material
Material and graphite collectively constitute.PAN microporous barrier envelopes manually modified polymer film A, can be used in normal water system ingredient environment.
During making the slurry agitation of negative electrode diaphragm, a certain amount of silicium cathode material for being coated with manually modified film is added.
Specific embodiment 6: present embodiment record be a kind of silicium cathode material containing surface modification film preparation
Method, the method comprises the following steps:
Step 1: polymer is dissolved into water, and the mass fraction of polymer is 0.1%~100%, and it is negative that silicon is added later
Pole heats while stirring at a temperature of 40~80 DEG C, removes the moisture in solution, or use spray drying process, removes moisture removal, obtain
The silicium cathode of the polymer film A of nanometer grade thickness must be coated with；The polymer be polyacrylate, carboxymethyl cellulose salt and
One or more of alginate；
Step 2: PEO (polyethylene glycol) is dissolved in THF (tetrahydrofuran) solvent, and stirring makes it completely dissolved, and matter is made
Measure the PEO solution that score is 0.1~100%；The silicium cathode for being coated with polymer film A that step 1 is obtained, conductive agent and
Lithium salts is added in PEO solution, heats while stirring at a temperature of 30~60 DEG C, removes the THF solvent in solution, or using spray
Mist seasoning removes THF solvent, obtains the silicium cathode material containing surface modification film, and the surface modification film is polymer film A
With PEO polymer solid electrolyte film.The conductive agent is carbons conductive agent, and the carbons conductive agent is acetylene black, conduction is poly-
Close one of object, carbon nanotube, graphene or multiple combinations；The lithium salts is selected from lithium hexafluoro phosphate LiPF6, double fluorine sulphonyl it is sub-
One of amine lithium, sulfuric acid difluoro lithium borate or combination.
Specific embodiment 7: a kind of system of the silicium cathode material containing surface modification film described in specific embodiment six
Preparation Method, in step 1, the polyacrylate is one of polyacrylic acid, Lithium polyacrylate or Sodium Polyacrylate；It is described
Carboxymethyl cellulose salt is sodium carboxymethylcellulose or carboxymethyl cellulose lithium；The alginate is sodium alginate, alginic acid
Lithium.
Specific embodiment 8: a kind of system of the silicium cathode material containing surface modification film described in specific embodiment six
Preparation Method, in step 1, the polymer/silicium cathode=2.0wt.%~100wt.%；The silicium cathode be silicon carbide or
Aoxidize sub- silicon.
Specific embodiment 9: a kind of system of the silicium cathode material containing surface modification film described in specific embodiment six
Preparation Method, in step 2, the PEO/ is coated with silicium cathode=0.5wt%~99wt% of polymer film A；The conductive agent
Content is 0.1wt%-8wt%；The content of the lithium salts is 0.05wt%-10wt%.
Specific embodiment 10: a kind of silicium cathode containing any specific embodiment preparation of specific embodiment six to nine
The lithium ion battery of material, the lithium ion battery are coiled lithium ion battery or stack type lithium ion battery；The lithium from
Sub- battery contains positive plate, negative electrode tab, isolation film, electrolyte or electrolyte, and the active material of the negative electrode tab is by silicium cathode material
Material and graphite composition.PEO solid electrolyte film envelopes manually modified polymer film A, can be used for normal water system ingredient environment
In.During making the slurry agitation of negative electrode diaphragm, a certain amount of silicium cathode material for being coated with manually modified film is added
Material.
Embodiment 1:
(1) it is accompanied with the preparation of the silicium cathode material S1 of manually modified film
PAA-Li (Lithium polyacrylate) is completely dissolved in aqueous solution, mass fraction 5%, is added aoxidizes sub- silicon later
SiO (PAA-Li/SiO=5.0wt%), heats while stirring at a temperature of 80 DEG C, removes the moisture in solution, is coated with
The oxidation Asia silicium cathode of the PAA-Li film of 50nm~100nm；
PAN (polyacrylonitrile) is dissolved in NMP (N-Methyl pyrrolidone) solvent, stirring makes it completely dissolved, and PAN is made
Solution, mass fraction 8%.Solution is added in the oxidation Asia silicium cathode for being coated with PAA-Li film and conductive agent (0.5wt%)
In (oxidation Asia silicon=8.0wt% that PAN/ is coated with PAA-Li film), heat while stirring at a temperature of 100 DEG C, remove solution
In nmp solvent, then obtain and be coated with the oxidation Asia silicium cathode material S1 of PAA-Li film and PAN microporous barrier.
(2) preparation of positive plate P1
Positive active material ternary nickel cobalt manganese NCM811, binder PVDF and conductive black are mixed, obtained through high-speed stirred
To finely dispersed mixture.In mixture, solid component include 95wt% NCM811,2wt% binder PVDF and
The conductive black of 3wt%.Mixture uses N-Methyl pyrrolidone that anode active material slurry is made as solvent, consolidates in slurry
Body content is 70wt%.The slurry is equably coated in aluminium foil two sides, is compacted by drying, roll squeezer, is obtained positive plate and be denoted as
P1。
(3) preparation of negative electrode tab N1
The oxidation Asia silicium cathode material S1 and artificial stone after PAA-Li film and PAN modified microporous membrane that (1) is obtained
The mixture of ink is mixed as active material, SBR class binder, thickener sodium carboxymethylcellulose and conductive agent conductive black,
It obtains being uniformly dispersed through high-speed stirred and the mixture containing negative electrode active material is made.In mixture, solid component includes
The artificial graphite of 90wt%, 5% PAA-Li film and PAN modified microporous membrane after oxidation sub- silicium cathode S1,1.5wt% carboxylic first
Base sodium cellulosate, 1.5wt% conductive black Super-P, 2wt% binder.Solvent is made using deionized water, cathode is made
Active material slurry, solid content is 50wt% in slurry.The slurry is equably coated in copper foil two sides, by drying, roll squeezer
Compacting, obtains negative electrode tab and is denoted as N1.
(4) assembling of battery C1
After positive plate P1, negative electrode tab N1 punching, plain battery is formed using Z-type lamination, produces aluminium pole ears and copper plating respectively
Nickel tab.Plain battery is clamped using glass clamp, the dynamics of glass clamp is 100MPa/m2, and in 85 DEG C of high-temperature vacuum bakings 24
Hour, then encapsulated with aluminum plastic film.Electrolyte uses the lithium hexafluorophosphate electrolyte solution containing 1M, and solvent is ethylene carbonate/carbonic acid two
Methyl esters/1,2 propylene carbonate, volume ratio are the mixed solvent of 1:1:1.Chemical conversion and aging are carried out to battery after encapsulation, obtained
Generous length is the rectangular flexible-packed battery of 140mm × 60mm × 6mm, is denoted as C1.
Embodiment 2:
This embodiment differs from embodiment 1 in that: the manually modified inner membrance of sub- silicium cathode material S1 is aoxidized by PAA-
Li is changed to carboxymethyl cellulose lithium CMC-Li, and the battery being prepared is C2.
Embodiment 3:
This embodiment differs from embodiment 1 in that: the manually modified inner membrance of sub- silicium cathode material S1 is aoxidized by PAA-
Li is changed to lithium alginate, and the battery being prepared is C3.
Embodiment 4:
This embodiment differs from embodiment 1 in that: the manually modified outer membrane for aoxidizing sub- silicium cathode material S1 is micro- by PAA
Pore membrane is changed to PEO solid electrolyte film, and the battery being prepared is C4.
Comparative example 1:
This comparative example difference from Example 1 is: solid component includes the PAA- of the artificial graphite of 90wt%, 5%
Oxidation Asia silicon S1 after Li film and PAN modified microporous membrane be changed to solid component include 95wt% artificial graphite, 5% it is unmodified
Oxidation Asia silicon, the battery being prepared be C5.
As shown in Fig. 2, C1, C2, C3, C4, compared with C5, cycle performance is significantly promoted, especially circulating battery early period declines
Subtract and obviously slow down, mainly since the presence of silicium cathode modified membrane forms good SEI film, while inhibiting silicon-carbon cathode
Circulation expansion.
As shown in figure 3, C1, C2, C3, C4, compared with C5, circulation expansion is reduced within 10% in 900 circles, and not
Modified silicon-carbon cathode battery, after the circle of circulation 300, circulation expansion has reached 20%.This shows the manually modified film of silicium cathode
It is significant to inhibition circulation expansion effect.Wherein, the test method of battery core circulation is that 45 DEG C of high temperature 1C charge to 4.2V, and constant pressure is extremely
Then 0.05C discharges into 2.5V with 1C, also, every 300 circle circulations, survey one-shot battery expanded thickness using PPG.
Claims (10)
1. a kind of preparation method of the silicium cathode material containing surface modification film, it is characterised in that: the method comprises the following steps:
Step 1: polymer is dissolved into water, and the mass fraction of polymer is 0.1%~100%, and silicon materials are added later,
It heats while stirring at a temperature of 40~80 DEG C, removes the moisture in solution, or use spray drying process, remove moisture removal, obtain
It is coated with the silicon materials of polymer film A；The polymer is one in polyacrylate, carboxymethyl cellulose salt and alginate
Kind is several；
Step 2: PAN is dissolved in nmp solvent, and stirring makes it completely dissolved, and it is 0.1%~100% that mass fraction, which is made,
PAN solution；The silicon materials for being coated with polymer film A and conductive agent that step 1 obtains are added in PAN solution, in 40~
It heats while stirring at a temperature of 120 DEG C, removes the nmp solvent in solution, or use spray drying process, remove nmp solvent, obtain
Silicium cathode material containing surface modification film, the surface modification film are polymer film A and PAN microporous barrier.
2. a kind of preparation method of silicium cathode material containing surface modification film according to claim 1, it is characterised in that:
In step 1, the polyacrylate is one of polyacrylic acid, Lithium polyacrylate or Sodium Polyacrylate；The carboxymethyl is fine
Tieing up plain salt is sodium carboxymethylcellulose or carboxymethyl cellulose lithium；The alginate is sodium alginate or lithium alginate.
3. a kind of preparation method of silicium cathode material containing surface modification film according to claim 1, it is characterised in that:
In step 1, the mass fraction of the polymer/silicon materials is 2.0%~100%；The silicon materials are nano-silicon, silicon carbide
Or aoxidize sub- silicon.
4. a kind of preparation method of silicium cathode material containing surface modification film according to claim 1, it is characterised in that:
In step 2, the PAN/ is coated with silicon materials=0.5wt%~99wt% of polymer film A；The content of the conductive agent is
0.1wt%~8wt%.
5. a kind of lithium ion battery of the silicium cathode material containing the preparation of Claims 1 to 4 any claim, feature exist
In: the lithium ion battery is coiled lithium ion battery or stack type lithium ion battery；The lithium ion battery contains anode
Piece, negative electrode tab, isolation film, electrolyte or electrolyte, the active material of the negative electrode tab is by common group of silicium cathode material and graphite
At.
6. a kind of preparation method of the silicium cathode material containing surface modification film, it is characterised in that: the method comprises the following steps:
Step 1: polymer is dissolved into water, and the mass fraction of polymer is 0.1%~100%, and silicium cathode is added later,
It heats while stirring at a temperature of 40~80 DEG C, removes the moisture in solution, or use spray drying process, remove moisture removal, obtain
It is coated with the silicium cathode of polymer film A；The polymer is one in polyacrylate, carboxymethyl cellulose salt and alginate
Kind is several；
Step 2: PEO is dissolved in THF solvent, and stirring makes it completely dissolved, and the PEO that mass fraction is 0.1~100% is made
Solution；The silicium cathode, conductive agent and lithium salts for being coated with polymer film A that step 1 is obtained are added in PEO solution, in 30
It heats while stirring at a temperature of~60 DEG C, removes the THF solvent in solution, or use spray drying process, remove THF solvent, obtain
To the silicium cathode material containing surface modification film, the surface modification film is polymer film A and PEO copolymer solid electrolyte
Film.
7. a kind of preparation method of silicium cathode material containing surface modification film according to claim 6, it is characterised in that:
In step 1, the polyacrylate is one of polyacrylic acid, Lithium polyacrylate or Sodium Polyacrylate；The carboxymethyl is fine
Tieing up plain salt is sodium carboxymethylcellulose or carboxymethyl cellulose lithium；The alginate is sodium alginate, lithium alginate.
8. a kind of preparation method of silicium cathode material containing surface modification film according to claim 6, it is characterised in that:
In step 1, the polymer/silicium cathode=2.0wt.%~100wt.%；The silicium cathode is that silicon carbide or oxidation are sub-
Silicon.
9. a kind of preparation method of silicium cathode material containing surface modification film according to claim 6, it is characterised in that:
In step 2, the PEO/ is coated with silicium cathode=0.5wt%~99wt% of polymer film A；The content of the conductive agent is
0.1wt%-8wt%；The content of the lithium salts is 0.05wt%-10wt%.
10. a kind of lithium ion battery of the silicium cathode material containing the preparation of claim 6~9 any claim, feature exist
In: the lithium ion battery is coiled lithium ion battery or stack type lithium ion battery；The lithium ion battery contains anode
The active material of piece, negative electrode tab, isolation film, electrolyte or electrolyte, the negative electrode tab is made of silicium cathode material and graphite.
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