CN106410267A - Silicon-based lithium ion secondary battery with high specific energy and preparation method of lithium ion secondary battery - Google Patents
Silicon-based lithium ion secondary battery with high specific energy and preparation method of lithium ion secondary battery Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to a silicon-based lithium ion secondary battery with high specific energy and a preparation method of the lithium ion secondary battery. The battery comprises a negative electrode, wherein the negative electrode comprises a negative electrode active material, a negative electrode binder and a negative electrode conductive additive; the negative electrode active material comprises one or more of silicon, silicon carbon, silicon (II) oxide and a silicon-based composite; the negative electrode binder comprises one or more of styrene-butadiene rubber, polyacrylic acid, sodium alginate and polyimide. According to the silicon-based lithium ion secondary battery with high specific energy and the preparation method of the lithium ion secondary battery, the prepared battery has high specific capacity and excellent cycle performance.
Description
Technical field
The present invention relates to lithium rechargeable battery is and in particular to a kind of high-energy-density silicon substrate lithium rechargeable battery and its system
Preparation Method.
Background technology
Lithium ion battery is main because its excellent performance has become various electronic products, wireless telecommunications and electric automobile etc.
Energy storage equipment.Commercial lithium-ion batteries mainly adopt graphite-like material with carbon element as negative electrode active material at present.However,
Carbons negative material is not high because of its specific capacity（372mAh/g）The safety issue brought with lithium deposition makes it can not meet electronics
Device miniaturization and automobile-used lithium ion cell high-capacity, long continuation of the journey require, thus research and develop the high energy of alternative carbons negative material
Metric density, high safety performance, the novel anode material of long circulation life are that can make a breakthrough one of lithium ion battery important
Factor.
Silicon as a kind of novel cathode material for lithium ion battery, because its theoretical specific capacity is high（4200mAh/g）And become and grind
Study carefully personnel's focus of attention.But its volumetric expansion present in charge and discharge process（400%）Active particle efflorescence can be caused, enter
And lead to capacity rapid decay because losing electrical contact, hinder its commercialization process.For solving this problem, people are carried out
Substantial amounts of exploration, including reducing silicon grain particle diameter, prepares silicon thin film and construction silicon based composite material etc..
Content of the invention
It is an object of the invention to provide a kind of high-energy-density silicon substrate lithium rechargeable battery and preparation method thereof, this battery
There is high-energy-density.
To achieve the above object, the present invention provides a kind of high-energy-density silicon substrate lithium rechargeable battery, including negative pole,
Described negative pole includes negative electrode active material, negative electrode binder and cathode conductive agent it is characterised in that described negative electrode active material is
Silicon, silicon-carbon, oxidation sub- one of silicon and silicon based composite material or multiple；Described negative electrode binder be butadiene-styrene rubber, poly- third
One of olefin(e) acid, sodium alginate, polyimides or multiple.
Above-mentioned high-energy-density silicon substrate lithium rechargeable battery, wherein, described high-energy-density silicon substrate lithium rechargeable battery is also
Including electrolyte, described electrolyte is the organic electrolyte system containing silicon substrate film for additive.
Above-mentioned high-energy-density silicon substrate lithium rechargeable battery, wherein, described silicon substrate film for additive is fluoro ethylene carbonate
One of ester, vinylene carbonate, 1,3- propane sultone or multiple.
Above-mentioned high-energy-density silicon substrate lithium rechargeable battery, wherein, described high-energy-density silicon substrate lithium rechargeable battery is also
Including positive pole, described positive pole includes positive active material, positive electrode binder and positive conductive agent；Described positive active material is height
Pressure cobalt acid lithium, nickel cobalt lithium aluminate, nickle cobalt lithium manganate, rich lithium multicomponent material one or more.
Another technical scheme that the present invention provides is a kind of preparation method of high-energy-density silicon substrate lithium rechargeable battery, bag
Include following steps：Step 1, makes positive plate；Step 2, makes negative plate, and wherein, the negative electrode active material of employing is silicon, silicon
Carbon, oxidation sub- one of silicon and silicon based composite material or multiple, the negative electrode binder of employing is butadiene-styrene rubber, polypropylene
One of acid, sodium alginate, polyimides or multiple；It is negative that step 3, the positive plate being obtained by step 1 and step 2 are obtained
Pole piece makes battery core；Step 4, battery core is put into external packing, removes the Residual water in battery core by baking；Step 5, to outsourcing
Electrolyte, vacuum-pumping and sealing is added, normal temperature turns quiescence in high temperature 12 hours after standing 12 hours in dress；Described electrolyte is containing silicon substrate
The organic electrolyte system of film for additive；Step 6, is melted into battery：First below 0.1C electric current charges to predetermined volumes
Afterwards, remove the gas in external packing；Then continue to charge to electric discharge after given voltage with 0.1C electric current, then charged with 0.1C electric current
Discharge to given voltage, after such charge and discharge cycles at least experience 3 times, remove the gas in external packing.
The preparation method of above-mentioned high-energy-density silicon substrate lithium rechargeable battery, wherein, described silicon substrate film for additive is fluorine
For one of ethylene carbonate, vinylene carbonate, 1,3- propane sultone or multiple.
The preparation method of above-mentioned high-energy-density silicon substrate lithium rechargeable battery, wherein, in described step 5, quiescence in high temperature divides
Two steps, a wherein rear step battery upper fixture.
The preparation method of above-mentioned high-energy-density silicon substrate lithium rechargeable battery, wherein, in described step 1, the positive pole of employing
Active material is high pressure cobalt acid lithium, nickel cobalt lithium aluminate, nickle cobalt lithium manganate, rich lithium multicomponent material one or more.
Compared with prior art, the present invention has the following technical effect that：
1）Employ positive pole and the negative material of height ratio capacity, so that the specific energy of lithium rechargeable battery is significantly improved;
2）Negative pole can regulate and control the addition of silica-base material according to the demand of battery specific energy, and by unique binding agent skill
Art, the negative plate of preparation has the advantages that height ratio capacity, high compacted density, stable to electrolyte solvent；
3）Due to the addition of special lithium salts and silicon substrate film for additive in electrolyte, make electrolyte have higher electrical conductivity and
The wellability good to material, enables electrolyte and cathode interface form the solid electrolyte interface film of densification simultaneously（SEI
Film）, make battery have preferable cycle characteristics；
4）Due to employing special standing and chemical synthesis technology, improve the efficiency first of silicon based cells, and ensure negative pole shape
While becoming to stablize fine and close SEI film, decrease bulking effect in cyclic process for the silica-base material.
Specific embodiment
The high-energy-density silicon substrate lithium rechargeable battery of the present invention includes positive pole, negative pole, barrier film, electrolyte and external packing.
Described positive pole includes positive active material（Mass fraction is 80wt% ~ 98.3wt%）, positive electrode binder（Mass fraction
For 1.2wt%-10wt%）With positive conductive agent（Mass fraction is 0.5wt%-10wt%）；Described positive active material is cobalt acid lithium
（Cobalt acid lithium containing high pressure）, LiMn2O4, LiFePO4, nickle cobalt lithium manganate, nickel cobalt lithium aluminate, one of rich lithium multicomponent material or
Multiple；Described positive electrode binder is HMW Kynoar；Described positive conductive agent is superconduction carbon black, crystalline flake graphite, carbon
Nanotube, graphite are dilute, one of carbon fiber or multiple.
In the present invention, positive active material have higher specific capacity, relatively low specific surface area, higher compacted density and
Preferably security performance.That thus prepares just has height ratio capacity, high compacted density, the advantage stable to electrolyte.Preferably
Ground, described positive active material is high pressure cobalt acid lithium, nickel cobalt lithium aluminate, nickle cobalt lithium manganate, one kind of rich lithium multicomponent material or
Multiple.
Described negative pole includes negative electrode active material（Mass fraction is 80wt% ~ 98wt%）, negative electrode binder（Mass fraction is
10wt%~2wt%）And cathode conductive agent（Mass fraction is 10wt% ~ 0wt%）；Described negative electrode active material is silicon, silicon-carbon, oxidation
Sub- silicon（SiOx）And one of silicon based composite material or multiple；Described negative electrode binder is butadiene-styrene rubber, polyacrylic acid, sea
One of mosanom, polyimides or multiple；Described cathode conductive agent is superconduction carbon black, CNT, graphite are dilute, carbon is fine
Dimension one of or multiple.
In the present invention, negative electrode binder has good adhesive property, can form chemical bond with negative electrode active material, and
There is excellent elasticity, negative pole in battery charging and discharging cyclic process can be born and expand and shrink the STRESS VARIATION brought, make electricity
Pond has excellent cycle performance.
Described barrier film is one of ceramic diaphragm, polyalkene diaphragm, nonwoven cloth diaphragm.
Described electrolyte is the organic electrolyte system containing silicon substrate film for additive.The solvent of described electrolyte is ethylene
One of alkene ester, propene carbonate, methyl ethyl carbonate or multiple mixtures.Described electrolyte needs to add silicon substrate
Film for additive, described silicon substrate film for additive（Mass fraction is 0.5wt% ~ 3wt%）For fluorinated ethylene carbonate, carbonic acid Asia second
One of alkene ester, 1,3- propane sultone or multiple；This silicon substrate film for additive can be formed surely on silicon-based anode surface
Fixed SEI film is it is ensured that the cyclical stability of battery.The electrolyte of described electrolyte is nonaqueous electrolyte it is preferred that described
Electrolyte is the lithium salts of non-aqueous solution, such as lithium hexafluoro phosphate（LiPF6）, lithium perchlorate（LiClO4）, dioxalic acid lithium borate
（LiBOB）One of or multiple.
The high-energy-density silicon substrate lithium rechargeable battery preparation method of the present invention comprises the steps of：
Step 1, by positive electrode binder and solvent（1-METHYLPYRROLIDONE）It is mixed together stirring, add positive conductive agent together
Stirring, is subsequently adding positive active material stirring and obtains solidliquid mixture, finally above-mentioned solidliquid mixture is evenly applied to aluminium
On paper tinsel surface, dry to obtain positive plate；
Step 2, by negative electrode binder and solvent（Deionized water）It is mixed together stirring, add cathode conductive agent and stir together,
It is subsequently adding negative electrode active material and stirs to obtain solidliquid mixture, finally above-mentioned solidliquid mixture is evenly applied to copper foil surface
On, dry to obtain negative plate；
Step 3, by step 1 be obtained positive plate and step 2 be obtained negative plate be cut into some small pieces respectively, by positive pole small pieces,
Barrier film, negative pole small pieces are piled up in the way of " Z " font successively, then couple together and weld aluminium flake by all positive pole small pieces, will
All negative pole small pieces couple together and weld nickel sheet or nickel plating copper sheet, and finally fixing both positive and negative polarity small pieces with adhesive tape makes it closely connect
Touch, that is, obtain battery core；
Step 4, battery core is put into external packing, removes the Residual water in battery core by baking；
Step 5, adds electrolyte, vacuum-pumping and sealing in external packing, turns quiescence in high temperature 12-24 after normal temperature standing 12-24 hour
Hour, make electrolyte fully infiltrate electrode slice（Including positive pole small pieces and negative pole small pieces）；
Described quiescence in high temperature in two steps, wherein after quiescence in high temperature 8-12 hour after a step battery upper fixture；Described quiescence in high temperature
Temperature is 60 DEG C～80 DEG C；
Step 6, is melted into battery（Segmentation is melted into）：First small current（Below 0.1C）After charging to predetermined volumes, remove outer
Gas in packaging；Then continue to charge to electric discharge after given voltage with 0.1C electric current, more specified electricity is charged to 0.1C electric current
Discharge after pressure, after such charge and discharge cycles at least experience 3 times, remove the gas in external packing, complete the high-energy-density of the present invention
The preparation of silicon substrate lithium rechargeable battery.
The high-energy-density silicon substrate lithium rechargeable battery preparation method of the present invention is using unique standing（Turn after normal temperature standing
For quiescence in high temperature）And chemical synthesis technology（Segmentation is melted into）It is ensured that it is the high efficiency first of battery, high power capacity, electrochemically stable
Property and the security of battery system.
Now high-energy-density silicon substrate lithium rechargeable battery of the present invention and preparation method thereof is illustrated with specific embodiment.
Embodiment 1：
93.5 grams of 1-METHYLPYRROLIDONEs and 6.52 grams of polyvinylidene fluoride are sufficiently mixed stirring, stir within 10 minutes mixed
The viscosity B coefficent closing liquid is less than 3%, adds 3.91 grams of scattered conductive carbon nanotubes, stirs the mixture within 10 minutes
Viscosity B coefficent be less than 3%, be eventually adding 250 grams of nickel cobalt aluminic acid lithium materials, stir the viscosity B coefficent of the mixture within 10 minutes
Less than 5%, then said mixture is uniformly coated on aluminium foil, 100 DEG C vacuum drying 24 hours after obtain positive plate.
148.5 grams of deionized waters and 2.63 grams of polyacrylic acid are sufficiently mixed stirring, stir the mixed liquor within 10 minutes
Viscosity B coefficent be less than 3%, add 1.05 grams of scattered conductive carbon nanotubes, stir within 10 minutes the viscous of mixture
Degree change is less than 3%, is eventually adding 100 grams of oxidation Asia silicon and graphite mixing material, stirs the viscosity of the mixture within 10 minutes
Change be less than 5%, then said mixture is uniformly coated on Copper Foil, 100 DEG C vacuum drying 24 hours after obtain negative pole
Piece.
The positive plate of making, negative plate are punched into respectively the small pieces of certain size, obtain some positive pole small pieces and negative pole
Small pieces, positive pole small pieces, barrier film, negative pole small pieces are alternately piled up successively, and weld aluminium strip on aluminium foil respectively, and Copper Foil welds nickel
Band, and finally fixed using adhesive tape, make the battery core that capacity is 2Ah.Then, battery core is put in external packing, after heat-sealing,
Toast in vacuum drying oven, remove the moisture of residual.Baking temperature be 70 DEG C, baking rear electrode piece water content 200ppm with
Under.
Baked battery core is cooled to room temperature in a vacuum, takes out, injection 5.5g contains tri- kinds of film forming of FEC/VC/PS to be added
The silicon substrate electrolyte of agent.Battery vacuum suction three times after fluid injection, each time 20min；Normal temperature turns high temperature 45 after standing 12 hours
DEG C standing 12 hours.
Before Battery formation, by battery upper fixture, it is melted into first 60 DEG C and stands 4 hours, chemical conversion temperature is 20 ± 3 DEG C, first
During charging, charge to the 10% of battery capacity with 0.02C electric current, and discharge the gas producing in charging process, then with 0.1C electric current
Discharge after continuing to charge to 4.2V, circulate 3 times（Refer to charge to electric discharge after 4.2V with 0.1C electric current）Afterwards by battery charge and discharge process
The gas of middle generation is extracted out, sealing.
Up to 90%, specific energy can reach the efficiency first of the silicon substrate lithium rechargeable battery prepared by this technique
270Wh/Kg.Improve specific energy, can be by increasing the content of silicon in negative pole.This battery, in the environment of 20 ± 3 DEG C, circulates
More than the 90% of initial capacity is still kept it was demonstrated that it possesses preferable cycle performance after 200 times.
Comparative example 1：
93.5 grams of 1-METHYLPYRROLIDONEs and 6.52 grams of polyvinylidene fluoride are sufficiently mixed stirring, stir within 10 minutes mixed
The viscosity B coefficent closing liquid is less than 3%, adds 3.91 grams of scattered conductive carbon nanotubes, stirs the mixture within 10 minutes
Viscosity B coefficent be less than 3%, be eventually adding 250 grams of nickel cobalt aluminic acid lithium materials, stir the viscosity B coefficent of the mixture within 10 minutes
Less than 5%, then said mixture is uniformly coated on aluminium foil, 100 DEG C vacuum drying 24 hours after obtain positive plate.
148.5 grams of deionized waters and 2.63 grams of polyacrylic acid are sufficiently mixed stirring, stir the mixed liquor within 10 minutes
Viscosity B coefficent be less than 3%, add 1.05 grams of scattered conductive carbon nanotubes, stir within 10 minutes the viscous of mixture
Degree change is less than 3%, is eventually adding 100 grams of oxidation Asia silicon and graphite mixing material, stirs the viscosity of the mixture within 10 minutes
Change be less than 5%, then said mixture is uniformly coated on Copper Foil, 100 DEG C vacuum drying 24 hours after obtain negative pole
Piece.
The positive plate of making, negative plate are punched into respectively the small pieces of certain size, obtain some positive pole small pieces and negative pole
Small pieces, positive pole small pieces, barrier film, negative pole small pieces are alternately piled up successively, and weld aluminium strip on aluminium foil respectively, and Copper Foil welds nickel
Band, and finally fixed using adhesive tape, make the battery core that capacity is 2Ah.Then, battery core is put in external packing, after heat-sealing,
Toast in vacuum drying oven, remove the moisture of residual.Baking temperature be 70 DEG C, baking rear electrode piece water content 200ppm with
Under.
Baked battery core is cooled to room temperature in a vacuum, takes out, inject 5.5 grams of general electrolytic liquid（EC：DEC=1：1,
1.0M LiPF6）, battery vacuum suction three times after fluid injection, each time 20min；It is quiet that normal temperature turns 45 DEG C of high temperature after standing 12 hours
Put 12 hours.
Before Battery formation, by battery upper fixture, it is melted into first 60 DEG C and stands 4 hours, chemical conversion temperature is 20 ± 3 DEG C, first
During charging, charge to the 10% of battery capacity with 0.02C electric current, and discharge the gas producing in charging process, then with 0.1C electric current
Discharge after continuing to charge to 4.2V, after circulating 3 times, the gas producing in battery charge and discharge process is extracted out, sealing.
The efficiency first of the silicon substrate lithium rechargeable battery of the general electrolytic liquid prepared by this technique is 83%, specific energy
It is only 245Wh/Kg.This battery, in the environment of 20 ± 3 DEG C, only keeps the 70% of initial capacity after circulation 100 times it was demonstrated that common
Electrolyte can not form the SEI film of negative terminal surface very well so as to efficiency, specific energy and cycle performance have significantly first
Decline.
Comparative example 2：
93.5 grams of 1-METHYLPYRROLIDONEs and 6.52 grams of polyvinylidene fluoride are sufficiently mixed stirring, stir within 10 minutes mixed
The viscosity B coefficent closing liquid is less than 3%, adds 3.91 grams of scattered conductive carbon nanotubes, stirs the mixture within 10 minutes
Viscosity B coefficent be less than 3%, be eventually adding 250 grams of nickel cobalt aluminic acid lithium materials, stir the viscosity B coefficent of the mixture within 10 minutes
Less than 5%, then said mixture is uniformly coated on aluminium foil, 100 DEG C vacuum drying 24 hours after obtain positive plate.
148.5 grams of deionized waters and 2.63 grams of polyacrylic acid are sufficiently mixed stirring, stir the mixed liquor within 10 minutes
Viscosity B coefficent be less than 3%, add 1.05 grams of scattered conductive carbon nanotubes, stir within 10 minutes the viscous of mixture
Degree change is less than 3%, is eventually adding 100 grams of oxidation Asia silicon and graphite mixing material, stirs the viscosity of the mixture within 10 minutes
Change be less than 5%, then said mixture is uniformly coated on Copper Foil, 100 DEG C vacuum drying 24 hours after obtain negative pole
Piece.
By make positive plate, negative plate be punched into the small pieces of certain size respectively, obtain some positive pole small pieces and negative
Minimum, positive pole small pieces, barrier film, negative pole small pieces are alternately piled up successively, and weld aluminium strip on aluminium foil respectively, and Copper Foil welds nickel
Band, and finally fixed using adhesive tape, make the battery core that capacity is 2Ah.Then, battery core is put in external packing, after heat-sealing,
Toast in vacuum drying oven, remove the moisture of residual.Baking temperature be 70 DEG C, baking rear electrode piece water content 200ppm with
Under.
Baked battery core is cooled to room temperature in a vacuum, takes out, injection 5.5g contains tri- kinds of film forming of FEC/VC/PS to be added
The silicon substrate electrolyte of agent.After fluid injection, battery normal temperature stands 24 hours.
Chemical conversion temperature is 20 ± 3 DEG C, charges to electric discharge after 4.2V with certain electric current, by battery charging and discharging mistake after circulating 3 times
The gas producing in journey is extracted out, sealing.
The efficiency first of the silicon substrate lithium rechargeable battery prepared by this technique is 80%, and specific energy can reach
240Wh/Kg.This battery is in the environment of 20 ± 3 DEG C, even if only keeping the 75% of initial capacity after circulating 100 times it was demonstrated that using
Silicon substrate electrolyte, does not adopt the special standing of the present invention and chemical synthesizing method, nor prepares high-energy-density, the silicon substrate of long continuation of the journey
Lithium rechargeable battery.
The high specific energy lithium rechargeable battery that the present invention provides, has the advantages that high-energy-density, cycle performance are good, Ke Yizuo
Alternative battery for consumer electronics and electric automobile and energy-storage battery.
Claims (8)
1. high-energy-density silicon substrate lithium rechargeable battery, including negative pole, described negative pole includes negative electrode active material, negative electrode binder
With cathode conductive agent it is characterised in that described negative electrode active material be silicon, in silicon-carbon, the sub- silicon of oxidation and silicon based composite material
One or more；Described negative electrode binder be one of butadiene-styrene rubber, polyacrylic acid, sodium alginate, polyimides or
Multiple.
2. high-energy-density silicon substrate lithium rechargeable battery as claimed in claim 1 is it is characterised in that described high-energy-density silicon substrate
Lithium rechargeable battery also includes electrolyte, and described electrolyte is the organic electrolyte system containing silicon substrate film for additive.
3. high-energy-density silicon substrate lithium rechargeable battery as claimed in claim 2 is it is characterised in that described silicon substrate film forming is added
Agent is one of fluorinated ethylene carbonate, vinylene carbonate, 1,3- propane sultone or multiple.
4. high-energy-density silicon substrate lithium rechargeable battery as claimed in claim 1 is it is characterised in that described high-energy-density silicon substrate
Lithium rechargeable battery also includes positive pole, and described positive pole includes positive active material, positive electrode binder and positive conductive agent；Described
Positive active material is high pressure cobalt acid lithium, nickel cobalt lithium aluminate, nickle cobalt lithium manganate, rich lithium multicomponent material one or more.
5. the preparation method of high-energy-density silicon substrate lithium rechargeable battery is it is characterised in that comprise the steps：
Step 1, makes positive plate；
Step 2, makes negative plate, and wherein, the negative electrode active material of employing is silicon, silicon-carbon, the sub- silicon of oxidation and silicon based composite material
One of or multiple, the negative electrode binder of employing is butadiene-styrene rubber, in polyacrylic acid, sodium alginate, polyimides one
Plant or multiple；
The negative plate that step 3, the positive plate being obtained by step 1 and step 2 are obtained makes battery core；
Step 4, battery core is put into external packing, removes the Residual water in battery core by baking；
Step 5, adds electrolyte, vacuum-pumping and sealing, normal temperature turns quiescence in high temperature 12 hours after standing 12 hours in external packing；
Described electrolyte is the organic electrolyte system containing silicon substrate film for additive；
Step 6, is melted into battery：After first below 0.1C electric current charges to predetermined volumes, remove the gas in external packing；So
Continue to charge to electric discharge after given voltage with 0.1C electric current afterwards, then electric discharge after given voltage is charged to 0.1C electric current, so fill
After discharge cycles at least experience 3 times, remove the gas in external packing.
6. the preparation method of high-energy-density silicon substrate lithium rechargeable battery as claimed in claim 5 is it is characterised in that described silicon
Base film for additive is one of fluorinated ethylene carbonate, vinylene carbonate, 1,3- propane sultone or multiple.
7. the preparation method of high-energy-density silicon substrate lithium rechargeable battery as claimed in claim 5 is it is characterised in that described step
In rapid 5, quiescence in high temperature in two steps, wherein after a step battery upper fixture.
8. the preparation method of high-energy-density silicon substrate lithium rechargeable battery as claimed in claim 5 is it is characterised in that described step
In rapid 1, the positive active material of employing is high pressure cobalt acid lithium, nickel cobalt lithium aluminate, nickle cobalt lithium manganate, one kind of richness lithium multicomponent material
Or it is multiple.
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| CN109585929A (en) * | 2018-10-10 | 2019-04-05 | 湖南立方新能源科技有限责任公司 | A kind of preparation method of silicon cathode lithium ion battery |
| CN109935832A (en) * | 2018-11-21 | 2019-06-25 | 万向一二三股份公司 | A kind of lithium ion battery silicon substrate negative electrode binder and the cathode piece preparation method using the binder |
| CN110649322A (en) * | 2019-09-03 | 2020-01-03 | 河南豫清新能源产业有限公司 | Method for manufacturing high-specific-energy lithium ion battery |
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