CN106159215A - A kind of silicium cathode material and preparation method thereof and include negative pole and the lithium ion battery of this silicium cathode material - Google Patents
A kind of silicium cathode material and preparation method thereof and include negative pole and the lithium ion battery of this silicium cathode material Download PDFInfo
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- 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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Abstract
The invention discloses the preparation method of a kind of silicium cathode material, the method includes: nano-silicon and liquid monomer is mixed, is uniformly dispersed, obtains the first suspension；By described first suspension and oil-soluble initiator mix homogeneously, obtain the second suspension；Under stirring condition, the aqueous solution by described second suspension with dissolved with dispersant is uniform, obtains the 3rd suspension；Under noble gas, described 3rd suspension is carried out polyreaction, obtains polymerizate；Described polymerizate, through filtering, washing and be dried, obtains desciccate；Under noble gas, described desciccate is carried out carbonization, obtain silicium cathode material.By technique scheme, the silicium cathode material that the present invention prepares improves the first charge-discharge efficiency of negative pole and the weight ratio capacity of lithium ion battery and cycle performance.
Description
Technical field
The present invention relates to a kind of cell negative electrode material and preparation method thereof and include this cell negative electrode material
Negative pole and lithium ion battery, in particular it relates to a kind of silicium cathode material and preparation method thereof and including
The negative pole of this silicium cathode material and lithium ion battery.
Background technology
At present, commercialization use lithium ion battery mainly use graphite as negative material, but graphite
Theoretical specific capacity be only 372 MAhs/g, therefore limit carrying further of lithium ion battery specific energy
High.Silicon has high theoretical lithium storage content (4200 MAhs/g) and low intercalation potential and standby because of it
Concerned.But, silica-base material is under the conditions of high level removal lithium embedded, owing to bigger expansion rate causes
Serious bulk effect, the cubical expansivity of silicon is 297%, and the biggest cubical expansivity result in electricity
The efflorescence rapidly in cyclic process of the middle active material, causes structural breakdown and the peeling of electrode material,
Make electrode material lose electrical contact, thus cause the cycle performance of electrode drastically to decline.
At present, the method to the modification of silica-base material and optimization be mainly silica-base material is doped and/
Or cladding, the method wherein using dopen Nano silicon materials, it is possible to improve following of battery to a certain extent
Ring performance, but owing to nano silicon material is easily reunited, after some recyclings, the circulation of battery
Performance easily deteriorates；The method using carbon coated Si sill, it is possible to reduce silicon and the side reaction of electrolyte,
Volumetric expansion during suppression silicon embedding lithium simultaneously, the method being coated with silica-base material at present mainly includes solid phase
Method, liquid phase method and infusion process etc., but the carbon-silicon composite material that these methods prepare, due to processing
Process needs the reasons such as ball milling pelletize, causes carbon-coated nano silicon in carbon-silicon composite material uneven and/or carbon
The problems such as ratio is low, when utilizing this carbon-silicon composite material to prepare battery cathode, it is impossible to meets and improves negative pole
The demand of first charge-discharge efficiency.
Therefore, in the urgent need to a kind of first charge-discharge efficiency that can improve battery cathode and lithium-ion electric
The silicium cathode material of pond specific capacity and cycle characteristics.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of silicium cathode material, the method includes: (1) will
Nano-silicon and liquid monomer mixing, be uniformly dispersed, obtain the first suspension；(2) suspend described first
Liquid and oil-soluble initiator mix homogeneously, obtain the second suspension；(3) under stirring condition, by described
Two suspensions and the aqueous solution dissolved with dispersant are uniform, obtain the 3rd suspension；(4) noble gas
Under, described 3rd suspension is carried out polyreaction, obtains polymerizate；(5) described polymerizate warp
Filter, wash and be dried, obtain desciccate；(6), under noble gas, described desciccate is carried out
Carbonization, obtains silicium cathode material；Wherein, in step (1), described liquid monomer be styrene and
Derivant, acrylate and derivant thereof, acrylamide and derivant thereof and vinylsiloxane and spread out
At least one in biology；And, relative to the nano-silicon of 100 weight portions, the consumption of described liquid monomer
For 200-5000 weight portion, the consumption of described oil-soluble initiator is 1-125 weight portion, described dispersant
Consumption be 1-250 weight portion.
The invention provides the silicium cathode material that method as defined above prepares.
Present invention also offers the negative pole of a kind of battery, this negative pole can include conducting base and be carried on this
The material layer on conducting base surface, wherein said material layer includes the silicium cathode prepared such as said method
Material.
Present invention also offers a kind of lithium ion battery, this lithium ion battery includes pole piece and non-aqueous solution electrolysis
Liquid, described pole piece and nonaqueous electrolytic solution seal in the cell housing, described pole piece include positive pole, negative pole and
Barrier film, wherein, described negative pole is negative pole as above.
By technique scheme, the preparation method of the present invention prepare a kind of silicium cathode material, should
When silicium cathode material is as the negative pole of battery, there is higher first charge-discharge efficiency, and this negative pole significantly carries
The weight ratio capacity of the high lithium ion battery being made up of this negative pole and cycle performance.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched
The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.
It is an object of the invention to provide the preparation method of a kind of silicium cathode material, the method includes: (1)
Nano-silicon and liquid monomer are mixed, is uniformly dispersed, obtains the first suspension；(2) hang described first
Supernatant liquid and oil-soluble initiator mix homogeneously, obtain the second suspension；(3) under stirring condition, by described
Second suspension and the aqueous solution dissolved with dispersant are uniform, obtain the 3rd suspension；(4) indifferent gas
Under body, described 3rd suspension is carried out polyreaction, obtains polymerizate；(5) described polymerizate
Through filtering, washing and be dried, obtain desciccate；(6), under noble gas, described desciccate is entered
Row carbonization, obtains silicium cathode material；Wherein, in step (1), described liquid monomer be styrene and
Its derivant, acrylate and derivant thereof, acrylamide and derivant thereof and vinylsiloxane and
At least one in derivant；And, relative to the nano-silicon of 100 weight portions, the use of described liquid monomer
Amount is 200-5000 weight portion, and the consumption of described oil-soluble initiator is 1-125 weight portion, described dispersion
The consumption of agent is 1-250 weight portion.
According to the present invention, inventor it was unexpectedly found that, using liquid monomer as the carbon source of coated Si before
Drive the starting material of body, use the oil-soluble initiator of special ratios, dispersant and nano-silicon to carry out suspension poly-
During conjunction, the silicon nanoparticle cladding of carbon source presoma parcel is more uniform, and wherein can wrap up many simultaneously
Individual nano-silicon, can only be coated with the situation of a nano-silicon accordingly, with respect to carbon source presoma, the present invention's
While silicium cathode material carbon is evenly coated, improve the content of silicon in unit volume silicium cathode material.Single
When in the volume silicium cathode material of position, silicone content is too high, although can promote the specific capacity of material, but simultaneously by
Excessive in volumetric expansion, carbon coating layer can be cracked, thus cause silicon active center and pole piece entirety to lose electricity
Contact, cycle performance deteriorates.When unit volume silicium cathode material silicon content is too low, although can obtain very well
Cycle performance, but material specific capacity is too low, reduces the energy density of battery, does not has use value.
It is provided simultaneously with height ratio capacity and the silicium cathode material of applicable cycle life, it is necessary to make unit bodies to obtain
In long-pending material, the content of silicon is in certain ratio, and is coated with complete.The present invention is by body before control carbon source
When body and the ratio of nano-silicon and formation complex emulsions, liquid pearl size can realize above-mentioned two requirement.Cause
This, the silicium cathode material that the method for the present invention prepares, can not only improve filling first of battery cathode
Discharging efficiency, additionally it is possible to improve lithium ion battery specific capacity and cycle characteristics.
According to the present invention, described in step (4), polymerizate is the nano-silicon being coated with carbon source presoma,
In order to improve the carbon ratio example in carbon source presoma further, to increase the amount of the surface coated carbon of nano-silicon,
Preferably, described styrene derivative includes styrene, divinylbenzene, fluorostyrene, methylbenzene
At least one in ethylene and p-methylstyrene；Described acrylate derivative includes methacrylic acid second
Ester, ethyl acrylate, butyl methacrylate, butyl acrylate, cyclohexyl methacrylate, propylene
Acid cyclohexyl, Isopropanediol dimethylacrylate, Isopropanediol diacrylate, butanediol dimethyl
Acrylate, butanediol diacrylate, triethoxy dimethylacrylate and triethoxy two propylene
At least one in acid esters；Described acrylamide derivative is N,N-DMAA；Described second
Alkenyl siloxane derivant includes VTES, tetramethyl divinyl disiloxane and four
At least one in methyl tetravinyl cyclotetrasiloxane.
According to the present invention, for avoiding carbon source presoma to occur partial melting to cause in intensification carbonisation
The carbon parcel on nano-silicon surface is uneven, under preferable case, can add crosslinkable list in liquid monomer
Body, to form insoluble polymer, the most described liquid monomer can be monofunctional monomer and polyfunctional group
The mixture of monomer, wherein, the weight ratio of described Monofunctional monomers and described multi-functional monomer is
1:0.1-10；Described Monofunctional monomers includes styrene, methyl styrene, p-methylstyrene, first
Base ethyl acrylate, ethyl acrylate, butyl methacrylate, butyl acrylate, methacrylic acid ring
In own ester, cyclohexyl acrylate, N,N-DMAA and VTES extremely
Few one, described polyfunctional monomer includes divinylbenzene, Isopropanediol dimethylacrylate, isopropyl
Omega-diol diacrylate, butanediol dimethylacrylate, butanediol diacrylate, triethoxy two
Methacrylate, triethoxy diacrylate, tetramethyl divinyl disiloxane and tetramethyl four
At least one in vinyl cyclotetrasiloxane, using the liquid monomer containing crosslinkable monomers as before carbon source
Driving the initial feed of body, the surface of the silicium cathode material obtained, carbon parcel uniformly, comprises this silicium cathode material
The negative pole of material, not only has higher first charge-discharge efficiency, and significantly improves and prepared by this negative pole
The weight ratio capacity of the lithium ion battery obtained and cycle performance.
According to the present invention, in order to the carbon source presoma making nano-silicon external sheath is more uniform, preferable case
Under, relative to the nano-silicon of 100 weight portions, the consumption of described liquid monomer is 250-2000 weight portion,
The consumption of described oil-soluble initiator is 2-50 weight portion, and the consumption of described dispersant is 1.5-100 weight
Part.
According to the present invention, the particle diameter of nano silicon material described in step (1) can be 20-200nm.
According to the present invention, oil-soluble initiator described in step (2) can be that those skilled in the art are ripe
The oil-soluble initiator known, such as, can be azo-initiator and/or peroxide, it is preferable that described
Oil-soluble initiator can include azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, peroxide
Change at least one in two caprinoyls and di-t-butyl peroxide.
According to the present invention, what dispersant described in step (3) can be well known to those skilled in the art divides
Powder, such as, can be neutral dispersing agent and/or ionic dispersant, it is preferable that described dispersant is permissible
Including polyvinyl alcohol, polyethylene glycol oxide, polyvinylpyrrolidone, sodium polyacrylate, detergent alkylate sulphur
At least one in acid sodium, sodium lauryl sulphate and cetyl quaternary ammonium salt.
According to the present invention, in order to the carbon source presoma making nano-silicon external sheath is more uniform, step (4)
Described in the condition of polyreaction include: reaction temperature is 60-90 DEG C, and the response time is 3-16 hour,
Preferably, in order to make the carbon source presoma of nano-silicon external sheath further evenly, reduce aggregation,
Increasing monomer conversion, described polyreaction carries out polyreaction at different temperatures, such as can be
React at 80 DEG C 2-4 hour, then react 1-12 hour at 85 DEG C；Or at 80 DEG C, react 1-2
Hour, then react at 85 DEG C 1-12 hour, then react 1-2 hour at 90 DEG C.
According to the present invention, the method making the carbon source presoma carbonization of nano-silicon outer cladding in step (6) can
Think carbonization method well known to those skilled in the art, such as, can be sintering and/or three sections of heating carbonizations,
Preferably, described carbonization method is three sections of heating carbonizations, and the condition of described three sections of heating carbonizations includes: the
The temperature of one section of heating carbonization is 100-450 DEG C, and the time is 2-4 hour；The temperature of second segment heating carbonization
Degree is for 550-750 DEG C, and the time is 2-4 hour；The temperature of the 3rd section of heating carbonization is 500-1300 DEG C,
Time is 2-6 hour, and described noble gas can be at least one in nitrogen, argon and helium.
The invention provides the silicium cathode material that method as above prepares.
Present invention also offers the negative pole of a kind of battery, this negative pole includes conducting base and is carried on this conduction
The material layer of matrix surface, wherein said material layer includes the silicium cathode material that said method prepares.
Wherein, described material layer can be prepared by following steps: by binding agent, solvent, conduction
Agent and above-mentioned silicium cathode material mixing are uniform, obtain cathode size；Described cathode size single spreading is existed
Conducting base surface, obtains cathode pole piece；Described cathode pole piece is dried, cutting, tabletting and punching
Cut out；The conductive agent that described conductive agent can be well known to those skilled in the art, such as can include white carbon black,
At least one in acetylene black, electrically conductive graphite, CNT, carbon fiber and Graphene；Described binding agent
The binding agent being well known to those skilled in the art, such as can include sodium carboxymethyl cellulose, butadiene-styrene rubber,
At least one in polyimides, polyvinylidene fluoride and polyurethane, described solvent is that effectively dissolving is above-mentioned
The solvent of binding agent, such as, can include at least in water, N-Methyl pyrrolidone, ethanol and acetone
Kind.
Wherein, in order to improve the battery performances such as the first charge-discharge efficiency of battery cathode, it is preferable that relatively
In the silicium cathode material of 100 weight portions, the consumption of described conductive agent is 0-20 weight portion, described bonding
The consumption of agent is 2-20 weight portion, and the consumption of described solvent is 60-600 weight portion；Described material layer
Thickness can be 20-300 micron.
Present invention also offers a kind of lithium ion battery, this lithium ion battery includes pole piece and non-aqueous solution electrolysis
Liquid, described pole piece and nonaqueous electrolytic solution seal in the cell housing, described pole piece include positive pole, negative pole and
Barrier film, wherein, described negative pole is negative pole as above.
Be further elaborated the present invention by the following examples.
Embodiment 1
It is the nano-silicon of 50nm, styrene and divinylbenzene mixing particle diameter, is uniformly dispersed, obtains the
One suspension, by above-mentioned first suspension and benzoyl peroxide mix homogeneously, obtains the second suspension.
Under stirring condition, by described second suspension and water-soluble dissolved with polyvinyl alcohol and dodecylbenzene sodium sulfonate
Liquid mix homogeneously, obtains the 3rd suspension, and the concentration of wherein said aqueous solution is 150g/L, relative to
The consumption of the nano-silicon of 100 weight portions, styrene and divinylbenzene is 500 weight portions, benzoyl peroxide first
The consumption of acyl is 7.5 weight portions, and the consumption of polyvinyl alcohol is 7.5 weight portions, dodecylbenzene sodium sulfonate
Consumption be 5 weight portions, wherein the amount ratio of styrene and divinylbenzene is 1:1.
Under a nitrogen atmosphere, described 3rd suspension is polymerized 2 hours at 80 DEG C, is polymerized 4 at 85 DEG C
Hour, 90 DEG C are polymerized 2 hours, obtain polymerizate, and this polymerizate, through filtering, is washed and is dried,
Obtain desciccate.Under a nitrogen atmosphere, above-mentioned desciccate heats 3 hours at 350 DEG C, at 650 DEG C
Heat 3 hours, heat 3 hours at 900 DEG C, obtain silicium cathode material.
By above-mentioned silicium cathode material, polyvinylidene fluoride, N-Methyl pyrrolidone and white carbon black mix homogeneously,
Obtain cathode size, by this cathode size single spreading at copper foil current collector (electrolytic copper foil, thickness: 12
Micron) surface, then drying, cutting, tabletting and stamping-out, obtain being loaded with the negative pole roundlet of material layer
Sheet, the wherein said a diameter of 1.3cm of negative pole sequin, the thickness of described material layer is 60 microns, wherein
Relative to the silicium cathode material of 100 weight portions, the consumption of described white carbon black is 3 weight portions, described poly-inclined two
The consumption of fluorothene is 5 weight portions, and the consumption of described N-Methyl pyrrolidone is 150 weight portions.
By LiPF6It is configured to LiPF with ethylene carbonate (EC) and diethyl carbonate (DEC)6Concentration
It is the solution (volume ratio of EC/DEC is 1:1) of 1.0 mol/L, obtains nonaqueous electrolytic solution.At hands
In casing, by above-mentioned negative pole sequin, polyethylene (PE) porous septum (commercially available from Dong Ran company, thickness
12um) and lithium sheet (purity be more than 99%) forms the button cell electrode meeting CR2016 specification degree:
Group.Above-mentioned electrode group is positioned in CR2016 button cell box hat, drips above-mentioned nonaqueous electrolytic solution,
Sealing obtains button cell, and it is to electrode half that gained button cell is above-mentioned negative pole sequin with lithium sheet
Battery.
Embodiment 2
Using preparation method same as in Example 1 to prepare half-cell, difference is, relative to 100
The consumption of the nano-silicon of weight portion, styrene and divinylbenzene is 400 weight portions, benzoyl peroxide
Consumption is 5 weight portions, and the consumption of polyvinyl alcohol is 6 weight portions, and the consumption of dodecylbenzene sodium sulfonate is
4 weight portions.
Embodiment 3
Using preparation method same as in Example 1 to prepare half-cell, difference is, relative to 100
The consumption of the nano-silicon of weight portion, styrene and divinylbenzene is 1500 weight portions, benzoyl peroxide
Consumption be 20 weight portions, the consumption of polyvinyl alcohol is 30 weight portions, the use of dodecylbenzene sodium sulfonate
Amount is 7 weight portions.
Embodiment 4
Using preparation method same as in Example 1 to prepare half-cell, difference is, described liquid
Monomer is butyl acrylate and butanediol diacrylate, and initiator is peroxidating di tert butyl carbonate, Qi Zhongxiang
Consumption for the nano-silicon of 100 weight portions, butyl acrylate and butanediol diacrylate is 300 weights
Amount part, the consumption of peroxidating di tert butyl carbonate is 7.5 weight portions, and the consumption of polyvinyl alcohol is 4 weight portions,
The consumption of dodecylbenzene sodium sulfonate is 1 weight portion.
Embodiment 5
Using preparation method same as in Example 1 to prepare half-cell, difference is, described liquid
Monomer is N,N-DMAA and butanediol diacrylate, and initiator is azodiisobutyronitrile,
Wherein relative to the nano-silicon of 100 weight portions, N,N-DMAA and butanediol diacrylate
The consumption of ester is 4500 weight portions, and the consumption of azodiisobutyronitrile is 120 weight portions, polyvinyl alcohol
Consumption is 180 weight portions, and the consumption of dodecylbenzene sodium sulfonate is 60 weight portions.
Embodiment 6
Using preparation method same as in Example 1 to prepare half-cell, difference is, described liquid
Monomer is styrene and divinylbenzene, and wherein the weight ratio of styrene and divinylbenzene is 1:0.2.
Embodiment 7
Using preparation method same as in Example 1 to prepare half-cell, difference is, described liquid
Monomer is styrene and divinylbenzene, and wherein the weight ratio of styrene and divinylbenzene is 1:9.
Embodiment 8
Using preparation method same as in Example 1 to prepare half-cell, difference is, relative to 100
The silicium cathode material of weight portion, the consumption of white carbon black is 1 weight portion, and the consumption of polyvinylidene fluoride is 2 weights
Amount part, the consumption of N-Methyl pyrrolidone is 100 weight portions.
Embodiment 9
Using preparation method same as in Example 1 to prepare half-cell, difference is, relative to 100
The silicium cathode material of weight portion, the consumption of white carbon black is 20 weight portions, and the consumption of polyvinylidene fluoride is 20
Weight portion, the consumption of N-Methyl pyrrolidone is 600 weight portions.
Embodiment 10
Using method same as in Example 1 to prepare half-cell, difference is, described material layer
Thickness is 20 microns.
Embodiment 11
Using method same as in Example 1 to prepare half-cell, difference is, described material layer
Thickness is 200 microns.
Comparative example 1
Using method same as in Example 1 to prepare half-cell, difference is, uses 2,2 '-idol
Nitrogen [2-(2-imidazoline-2-base) propane] dihydrochloride substitutes benzoyl peroxide, uses polyvinyl pyrrole
Alkanone (Mw=350,000g/mol) substitutes polyvinyl alcohol and dodecylbenzene sodium sulfonate.
Comparative example 2
Using method same as in Example 1 to prepare half-cell, difference is, uses uncoated
The silicium cathode material prepared in nano-silicon alternate embodiment 1.
Comparative example 3
Using method same as in Example 1 to prepare half-cell, difference is, uses by following
The silicium cathode material prepared in the carbon-coated nano silicon alternate embodiment 1 that step prepares.
By nano-silicon and the aqueous solution of polyvinyl alcohol, it is uniformly dispersed, evaporation of solvent, it is coated with
Having the nano-silicon of polyvinyl alcohol, wherein the amount ratio of nano-silicon and polyvinyl alcohol is 1:5, polyvinyl alcohol
The concentration of aqueous solution is 100g/L；Under condition of nitrogen gas, products therefrom, through carbonization, obtains the nanometer of carbon cladding
Silicon.
Comparative example 4
Using method same as in Example 1 to prepare half-cell, difference is, relative to 100 weights
The nano-silicon of amount part, the consumption of styrene and divinylbenzene is 150 weight portions, the use of benzoyl peroxide
Amount is 1.5 weight portions, and the consumption of polyvinyl alcohol is 1.5 weight portions, the consumption of dodecylbenzene sodium sulfonate
It it is 1 weight portion.
Comparative example 5
Using method same as in Example 1 to prepare half-cell, difference is, relative to 100 weights
The nano-silicon of amount part, the consumption of styrene and divinylbenzene is 5100 weight portions, benzoyl peroxide
Consumption is 100 weight portions, and the consumption of polyvinyl alcohol is 180 weight portions, the use of dodecylbenzene sodium sulfonate
Amount is 60 weight portions.
Testing example 1
The battery of the half-cell that this testing example obtains in testing example 1-11 and comparative example 1-5
Cycle performance.
At 25 DEG C, by the half-cell that obtains in embodiment 1-11 and comparative example 1-5 (with metal lithium sheet
Negative material current potential as the lithium rechargeable battery of anode is higher than anodic potentials, it is therefore desirable to first discharge
Recharge) with 0.15mA/cm2Electric current density be discharged to 0.05V, after shelving 30 minutes with
0.15mA/cm2Electric current density charge to 2.5V, the discharge capacity first of record battery and initial charge
Capacity.Discharge with actual capacity 0.3C again, and charge with actual capacity 0.3C.
Repeating discharge and recharge 200 times, the electric discharge after record circulating battery 50,100,150 and 200 times is held
Amount, and calculate the weight of the first charge-discharge efficiency of battery, capability retention and battery according to the following equation
Specific capacity:
The discharge capacity of first charge-discharge efficiency=initial charge capacity (de-lithium) (MAH)/first is (embedding
Lithium) (MAH).
N times capability retention (%)=(electric discharge of the discharge capacity/circulate first of n-th circulation is held
Amount) × 100%.
Weight ratio capacity (MAh/g)=it is battery discharge capacity first (MAH)/negative pole tablet weight
Amount.
Result is as shown in table 1.
Table 1
Data from table 1 are it can be seen that the filling first of the half-cell that prepared by embodiment 1-11
Discharging efficiency is all more than 85%, i.e. the irreversible capacity of negative pole is less, after circulation 100 times, and battery
The sustainment rate of capacity all can be maintained at more than 85%, and after circulating 200 times, the sustainment rate of battery capacity is equal
More than 80% can be maintained at, be significantly better than that the half-cell prepared in comparative example 1-5, and at head
After secondary charge and discharge cycles, battery has higher weight ratio capacity simultaneously.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
Execute the detail in mode, in the technology concept of the present invention, can be to the technical side of the present invention
Case carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technology described in above-mentioned detailed description of the invention is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not
The repetition wanted, various possible compound modes are illustrated by the present invention the most separately.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as its
Without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (12)
1. a preparation method for silicium cathode material, the method includes:
(1) nano-silicon and liquid monomer are mixed, be uniformly dispersed, obtain the first suspension；
(2) by described first suspension and oil-soluble initiator mix homogeneously, the second suspension is obtained；
(3), under stirring condition, the aqueous solution by described second suspension with dissolved with dispersant is uniform,
Obtain the 3rd suspension；
(4), under noble gas, described 3rd suspension is carried out polyreaction, obtains polymerizate；
(5) described polymerizate is through filtering, washing and be dried, and obtains desciccate；
(6) under noble gas, described desciccate is carried out carbonization, obtain silicium cathode material；
Wherein, in step (1), described liquid monomer be Styrene and its derivatives, acrylate and
At least one in its derivant, acrylamide and derivant thereof and vinylsiloxane and derivant thereof；
And, relative to the nano-silicon of 100 weight portions, the consumption of described liquid monomer is 200-5000 weight portion,
The consumption of described oil-soluble initiator is 1-125 weight portion, and the consumption of described dispersant is 1-250 weight
Part.
Preparation method the most according to claim 1, it is characterised in that described styrene derivative
Including in styrene, divinylbenzene, fluorostyrene, methyl styrene and p-methylstyrene extremely
Few one；Described acrylate derivative includes ethyl methacrylate, ethyl acrylate, metering system
Acid butyl ester, butyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, Isopropanediol dimethyl
Acrylate, Isopropanediol diacrylate, butanediol dimethylacrylate, butanediol diacrylate
At least one in ester, triethoxy dimethylacrylate and triethoxy diacrylate；Described third
Alkenylamide derivative is N,N-DMAA；Described vinylsiloxane derivant includes ethylene
In ethyl triethoxy silicane alkane, tetramethyl divinyl disiloxane and t etram-ethyltetravinylcyclotetrasiloxane
At least one.
Preparation method the most according to claim 1, it is characterised in that described liquid monomer is single
Monomer and the mixture of polyfunctional monomer, wherein, described Monofunctional monomers and described many officials
The weight ratio of energy single group body is 1:0.1-10；Described Monofunctional monomers includes styrene, methylbenzene second
Alkene, p-methylstyrene, ethyl methacrylate, ethyl acrylate, butyl methacrylate, propylene
Acid butyl ester, cyclohexyl methacrylate, cyclohexyl acrylate, N,N-DMAA and ethylene
At least one in ethyl triethoxy silicane alkane, described polyfunctional monomer includes divinylbenzene, Isopropanediol
Dimethylacrylate, Isopropanediol diacrylate, butanediol dimethylacrylate, butanediol two
Acrylate, triethoxy dimethylacrylate, triethoxy diacrylate, tetramethyl divinyl
At least one in base disiloxane and t etram-ethyltetravinylcyclotetrasiloxane.
Preparation method the most according to claim 1, it is characterised in that relative to 100 weight portions
Nano-silicon, the consumption of described liquid monomer is 250-2000 weight portion, described oil-soluble initiator
Consumption is 2-50 weight portion, and the consumption of described dispersant is 1.5-100 weight portion.
Preparation method the most according to claim 1, it is characterised in that in step (1), described
The particle diameter of nano-silicon is 20-200nm.
Preparation method the most according to claim 1, it is characterised in that in step (2), described
Oil-soluble initiator includes azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, peroxidating two
At least one in caprinoyl and di-t-butyl peroxide.
Preparation method the most according to claim 1, it is characterised in that in step (3), described
Dispersant includes polyvinyl alcohol, polyethylene glycol oxide, polyvinylpyrrolidone, sodium polyacrylate, dodecane
At least one in base benzene sulfonic acid sodium salt, sodium lauryl sulphate and cetyl quaternary ammonium salt.
Preparation method the most according to claim 1, it is characterised in that in step (4), described
The condition of polyreaction includes: reaction temperature is 60-90 DEG C, and the response time is 3-16 hour.
Preparation method the most according to claim 1, it is characterised in that in step (6), described
Carbonization is three sections of heating carbonizations, and the condition of three sections of heating carbonizations includes: the temperature of first paragraph heating carbonization is
100-450 DEG C, the time is 2-4 hour；The temperature of second segment heating carbonization is 550-750 DEG C, and the time is
2-4 hour；The temperature of the 3rd section of heating carbonization is 500-1300 DEG C, and the time is 2-6 hour.
10. the silicium cathode material prepared according to the method described in any one in claim 1-9.
The negative pole of 11. 1 kinds of batteries, wherein, this negative pole includes conducting base and is carried on this conducting base
The material layer on surface, it is characterised in that described material layer includes the silicium cathode material described in claim 10
Material.
12. 1 kinds of lithium ion batteries, this lithium ion battery includes pole piece and nonaqueous electrolytic solution, described pole piece
Sealing in the cell housing with nonaqueous electrolytic solution, described pole piece includes positive pole, negative pole and barrier film, its feature
Being, described negative pole is the negative pole described in claim 11.
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| CN107086305A (en) * | 2017-04-24 | 2017-08-22 | 广东烛光新能源科技有限公司 | A kind of silicon-carbon cathode material and preparation method thereof |
| CN111769266A (en) * | 2020-06-23 | 2020-10-13 | 合肥国轩高科动力能源有限公司 | Silicon-based negative electrode material and lithium ion battery containing same |
| CN114284556A (en) * | 2020-09-18 | 2022-04-05 | 浙江蓝天环保高科技股份有限公司 | Lithium ion battery electrolyte and lithium ion quick-charging battery |
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