CN108767328A - A kind of preparation method of all-solid lithium-ion battery - Google Patents
A kind of preparation method of all-solid lithium-ion battery Download PDFInfo
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- CN108767328A CN108767328A CN201810504823.6A CN201810504823A CN108767328A CN 108767328 A CN108767328 A CN 108767328A CN 201810504823 A CN201810504823 A CN 201810504823A CN 108767328 A CN108767328 A CN 108767328A
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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
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
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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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- 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
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Abstract
The invention discloses a kind of preparation methods of all-solid lithium-ion battery, are related to field of lithium ion battery.Including：By the polymer monomer that mass ratio is 10-30%, the additive of the lithium salts of 1-10%, the initiator of 0.001-5%, 0.001-5% is dissolved in organic solvent, is prepared into polymer dielectric；Polymer-the positive electrode active materials that will be sequentially prepared by the polymer dielectric, polymer-negative electrode active material and polymer dielectric-inorganic filler are mixed, and are stirred at a set temperature and ultrasonic vibration, and electrostatic spinning liquid is obtained；The electrostatic spinning is subjected to electrostatic spinning with liquid, prepares positive plate and negative plate respectively on the receiver for be covered with collector, fiber membrane is prepared on the receiver for being covered with the negative plate or the positive plate；By the positive plate, the fiber membrane and the negative plate are sequentially overlapped and are prepared into battery core, by the battery core through hot pressing, seal, and all-solid lithium-ion battery is made after shaping and degasification in chemical conversion.
Description
Technical field
The present invention relates to field of lithium ion battery, more particularly relate to a kind of preparation method of all-solid lithium-ion battery.
Background technology
Lithium ion battery is a kind of high-energy-density, and low self-discharge, the chemical power device of long-life is most to compete now
One of electrochemical energy storage technology of power still has higher development potentiality following.The lithium-ion electric of commercial applications at present
The widely used liquid electrolyte in pond is to provide outstanding conductivity and chemical property, but since used liquid electrolyte has
There is the features such as high volatile, low ignition point, during lithium ion battery technology meets high rate performance and high-energy density, is easy
When in use because of high current charge-discharge, electrolyte occurs and generates heat spontaneous combustion so that causing the problems such as super-charge super-discharge, internal short-circuit
The safety problems such as on fire from explosion.In addition the lithium ion battery bad mechanical property for using liquid electrolyte, generally to sacrifice in engineering
Performance is that cost promotes its mechanical performance.In order to solve these problems, the solid-state of safety and mechanical performance can significantly be promoted
Electrolyte lithium-ion battery receives more and more attention.
Solid state electrolysis Quality Research can meet the needs of lithium ion battery, solid state electrolysis Quality Research master substantially at present
It concentrates on polymer dielectric and inorganic solid electrolyte.For polymer dielectric, chemical property is outstanding, chemistry
Stability is good, is easy to cure and remold, has certain mechanical performance and be not easy embrittlement, and can be compatible with a variety of lithium salts,
Lithium ion transference number can also control, but polymer dielectric also because its glass transition temperature is close to room temperature have it is more
Crystalline phase, to which its ionic conductivity differs larger with liquid electrolyte, the simple lithium ion battery for applying polymer dielectric
Internal resistance is larger.For inorganic solid electrolyte, conductivity is high, and mechanical performance is outstanding, but with electrode active material compatibility
Difference, easy embrittlement also limit its application.
In addition, being directed to general lithium ion battery plus-negative plate active material painting method, solid electrolyte is lived with positive and negative anodes
The contact of property substance can constantly deteriorate during the use of battery, to slacken the performance and used life of lithium ion battery.
For the problem, current general scheme is to apply gel electrolyte, but gel electrolyte still applies a small amount of liquid electric
Xie Zhi does not solve the above problems fundamentally in use it also occur that analysing liquid and failing.
Invention content
The embodiment of the present invention provides a kind of preparation method of all-solid lithium-ion battery, provides a kind of solid electrolyte and electricity
Pole material well contacts, high-mechanical property, high conductivity, the production method of the all-solid lithium-ion battery of high security.
The embodiment of the present invention provides a kind of preparation method of all-solid lithium-ion battery, including：
By the polymer monomer that mass ratio is 10-30%, the lithium salts of 1-10%, the initiator of 0.001-5%, 0.001-
5% additive is dissolved in organic solvent, is prepared into polymer dielectric；
Polymer-the positive electrode active materials that will be sequentially prepared by the polymer dielectric, polymer-negative electrode active material
Material and polymer dielectric-inorganic filler are mixed, and are stirred at a set temperature and ultrasonic vibration, and Static Spinning is obtained
Silk liquid；
The electrostatic spinning is subjected to electrostatic spinning with liquid, prepares positive plate respectively on the receiver for be covered with collector
And negative plate, prepare fiber membrane on the receiver for being covered with the negative plate or the positive plate；
By the positive plate, the fiber membrane and the negative plate are sequentially overlapped and are prepared into battery core, and the battery core is passed through
Hot pressing is sealed, and all-solid lithium-ion battery is made after shaping and degasification in chemical conversion.
Preferably, described by the polymer monomer that mass ratio is 10-30%, the lithium salts of 1-10%, the initiation of 0.001-5%
The additive of agent, 0.001-5% is dissolved in organic solvent, is prepared into polymer dielectric, is specifically included：
By the polymer monomer that mass ratio is 10-30%, the lithium salts of 1-10%, the initiator of 0.001-5%, 0.001-
5% additive is dissolved in organic solvent, is prepared into polymer dielectric presoma；Made polymer dielectric presoma is passed through
Polymerization, which causes, is prepared into the polymer dielectric；The polymerization initiation includes the thermal initiation of 10-200 DEG C of temperature；Or cause
The microwave of power 0-1000W causes；Or emission wavelength 250-400nm, power 10-2000W's is light-initiated；Or voltage 0-
The electricity of 10V, electric current 1-1000mA cause.
Preferably, described that the positive plate, the fiber membrane and the negative plate are sequentially overlapped and are prepared into battery core, tool
Body includes：
By the positive plate, the fiber membrane and the negative plate are sequentially overlapped, and will be before the polymer dielectric
It drives body and is filled in the positive plate, between the fiber membrane and the negative plate, battery core is prepared by polymerizeing to cause.
Preferably, the polymer-positive electrode active materials that will be sequentially prepared by the polymer dielectric, polymerization
Before object-negative electrode active material and polymer dielectric-inorganic filler are mixed, further include：
By conducting polymer, the polymer dielectric is dissolved in the organic solvent and is made respectively with positive electrode, mixing
For at polymer-positive electrode active materials；
By conducting polymer, the polymer dielectric is dissolved in the organic solvent and is made respectively with negative material, mixing
For at polymer-negative electrode active material；
The polymer dielectric is dissolved in the organic solvent and is prepared by mixing into polymer dielectric-with inorganic filler
Inorganic filler；
It is described to be stirred in the case where setting whipping temp and ultrasonic vibration, electrostatic spinning liquid is obtained, is specifically included：
At room temperature by the polymer-positive electrode active materials, the conducting polymer-negative electrode active material and described poly-
After polymer electrolyte-inorganic filler stirring 1-10h, by ultrasonic vibration, electrostatic spinning liquid is obtained；The setting whipping temp
10-50 DEG C, the ultrasonic vibration time 0.5-5h.
Preferably, the conducting polymer is polythiophene, polypyrrole, polyacetylene, polyaniline and these four conducting polymers
Derivative in one kind or and several；
The positive electrode includes LiFePO4, lithium manganese phosphate, cobalt acid lithium, LiMn2O4, lithium nickelate, nickel-cobalt-manganese ternary, nickel
One or more combinations in cobalt aluminium ternary, nickel manganese binary material；
The negative material includes natural graphite, artificial graphite, silica-base material, hard carbon, metal complex frame clsss cathode
One or more combinations in material；
The inorganic filler is Ca-Ti ore type, NASICON types, LISICON types, carbuncle type metal oxide, metal sulphur
One kind in compound.
Preferably, described that the electrostatic spinning is subjected to electrostatic spinning with liquid, divide on the receiver for be covered with collector
Positive plate and negative plate are not prepared, it is thin to prepare fiber on the receiver for being covered with the negative plate or the positive plate
Film specifically includes：
The electrostatic spinning is subjected to electrostatic spinning with liquid, is connecing for the aluminium foil between 100nm-5 μm being covered with thickness
It receives and obtains positive plate on device, wherein electrostatic spinning voltage is 25kV, 25 DEG C, injection speed 0.2mL/h of electrostatic spinning temperature, spray
Mouth movement speed 15mm/s；
The electrostatic spinning is subjected to electrostatic spinning with liquid, is connecing for the copper foil between 100nm-5 μm being covered with thickness
It receives and obtains negative plate on device, wherein electrostatic spinning voltage 20kV, 25 DEG C, injection speed 0.1mL/h of electrostatic spinning temperature, spout
Movement speed 30mm/s；
The electrostatic spinning is subjected to electrostatic spinning with liquid, thickness is obtained on the receiver for be covered with negative plate is
Fiber membrane between 200nm-50 μm, wherein electrostatic spinning voltage 20kV, 25 DEG C of electrostatic spinning temperature, injection speed
0.2mL/h, spout movement speed 30mm/s.
Preferably, the polymer monomer includes the one or more of following substance and its derivative：EO,MMA,VDF,
VC,PC,BA,AN,TMV,PO；
The lithium salt material includes LiPF6、LiBOB、LiBF4、LiTFSI、LiClO4At least one of；
The initiator is at least one of organic peroxide class, azo, redox type free base initiator；
The additive is one or more combinations in plasticiser, surfactant, fire retardant, dispersant；
The organic solvent is ethyl alcohol, acetone, isopropanol, petroleum ether, acetonitrile, carbonates, amides, N- methylpyrroles
Alkanone, dimethyl sulfoxide (DMSO), N- ethyl pyrrolidones, one kind in triethylamine or combination.
The embodiment of the present invention provides a kind of preparation method of all-solid lithium-ion battery, including：It is 10-30% by mass ratio
Polymer monomer, the additive of the lithium salts of 1-10%, the initiator of 0.001-5%, 0.001-5% is dissolved in organic solvent,
It is prepared into polymer dielectric；Polymer-the positive electrode active materials that will be sequentially prepared by the polymer dielectric, polymerization
Object-negative electrode active material and polymer dielectric-inorganic filler are mixed, and are stirred at a set temperature and ultrasound is shaken
It swings, obtains electrostatic spinning liquid；The electrostatic spinning is subjected to electrostatic spinning with liquid, is divided on the receiver for be covered with collector
Positive plate and negative plate are not prepared, it is thin to prepare fiber on the receiver for being covered with the negative plate or the positive plate
Film；By the positive plate, the fiber membrane and the negative plate are sequentially overlapped and are prepared into battery core, by the battery core through hot pressing,
Sealing, chemical conversion, all-solid lithium-ion battery is made after shaping and degasification.The production method, making step is simple, cost of manufacture
It is low.The battery consistency prepared by this method is good, and high mechanical strength, security performance are high, the capacity attenuation in charge and discharge process
It is few, it can be applied to demand large capacity, high security, high-power use occasion.
Description of the drawings
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
Obtain other attached drawings according to these attached drawings.
Fig. 1 is the combination schematic diagram of battery core provided in an embodiment of the present invention；
Fig. 2 is the SEM figures of the electrospun fibers film prepared by slurry 1 in the embodiment of the present invention one；
Fig. 3 is the charging and discharging curve schematic diagram for the assembled battery that the embodiment of the present invention one provides；
Fig. 4 is the cycle performance curve synoptic diagram for the assembled battery that the embodiment of the present invention one provides.
Specific implementation mode
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation describes, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Embodiment one
Step 101：By 80g MMA, 25g LiTFSI, 0.04g azodiisobutyronitriles initiator, 1g phthalic acid diformazans
Ester plasticiser is dissolved in 10ml ethylene carbonates, polymer dielectric presoma is made in 10ml dimethyl carbonate mixed solvents；By institute
Polymer dielectric presoma processed reacts 30min in 80 DEG C of water-baths and polymer dielectric is made.
Step 102：400 mesh sieve will be crossed after LiFePO4, natural graphite, acetylene black, the grinding of LLZO ceramic electrolytes.It will
0.1g polyvinylpyrrolidones dispersant, 0.1g polypyrrole conducting polymers are dissolved in 4ml N-Methyl pyrrolidones and dispersion are made
Liquid；Anode sizing agent will be made after 0.8g LiFePO4s, the grinding of 0.1g acetylene blacks；0.8g natural graphites, 0.1g acetylene blacks are ground
After be dissolved in and be mixed and made into negative electrode slurry with made dispersion liquid.By the anode sizing agent of aforementioned preparation and dispersion liquid 1:1 is mixed and made into slurry
Material 1；Negative electrode slurry and dispersion liquid 1:1 is mixed and made into slurry 2.Polymer dielectric described in 0.4g step 1 is dissolved in 2ml carbonic acid
Vinyl acetate and 2ml dimethyl carbonates in the mixed solvent simultaneously add 0.1g polyvinylpyrrolidones dispersant, 0.5g LLZO ceramic electricals
Slurry 3 is made in solution matter inorganic filler.And by made three kinds of slurries agitated 10h at room temperature, electrostatic is obtained respectively after ultrasonic 1h
Spinning liquid.
Step 103：Step 102 gained electrostatic spinning is subjected to electrostatic spinning with liquid, on being covered with the receiver of aluminium foil
Positive plate afterwards, voltage is 25kV, spout and receiver distance 10cm, spinning solution and environment temperature 25 between spout and receiver
DEG C, spout injection speed 0.2mL/h, spout movement speed 15mm/s.
When step 102 gained electrostatic spinning is carried out electrostatic spinning with liquid, born on the receiver for be covered with copper foil
Pole piece, voltage is 20kV, spout and 25 DEG C of receiver distance 5cm, spinning solution and environment temperature, spout note between spout and receiver
Firing rate degree 0.1mL/h, spout movement speed 30mm/s.
Step 102 gained electrostatic spinning is subjected to electrostatic spinning with liquid, is received on the receiver for be covered with negative plate
Rice fibre electrolyte film, voltage is 20kV, spout and receiver distance 10cm, spinning solution and environment temperature between spout and receiver
25 DEG C, spout injection speed 0.2mL/h, spout movement speed 30mm/s.
Step 104：Positive plate, negative plate, the nanofiber dielectric film that step 103 is obtained, 60 DEG C in drying box
Dry 5h, is made button cell battery core, polymer dielectric prepared by step 101 after then being combined with sequence shown in FIG. 1
Presoma in syringe filling road battery core with being allowed to just flood nano-fiber film and positive plate, negative plate completely, in argon gas
Battery core is made after reacting 5h annealing under environment, in 110 DEG C of temperature.
Step 105：The made battery core of step 104 is cut into after the disk of diameter 18mm at 80 DEG C through 10kgf/cm2Pressure
Compression moulding under power assembles button cell with the sequence of anode cover, battery core, gasket, shrapnel, negative electrode casing after cooling and seals acquisition
Addition monomers battery.
Embodiment two
Step 201, by 50g EO, 10g LiClO4, 3g vinyltriethoxysilane fire retardant, 0.1g FeCl3Cause
Agent is dissolved in 10ml ethylene carbonates, polymer dielectric presoma is made in 10ml dimethyl carbonate mixed solvents；In microwave reaction
The microwave power for applying 300W in device causes polymerization 60s, and polymer dielectric is made.
Step 202, it is dissolved in 4ml N-Methyl pyrrolidones by the made polymer dielectric 0.4g of step 201 and dispersion is made
Liquid；Positive electrode active materials 0.8g LiMn2O4s, conductive agent 0.1g acetylene blacks；Negative electrode active material selects 0.7g hard carbons, conductive
Slurry 1 and slurry 2 is respectively prepared according to the method for embodiment one in agent 0.15g acetylene blacks.It will polymerize described in 0.1g steps 201
Object electrolyte is dissolved in 2ml ethylene carbonates and 2ml dimethyl carbonates in the mixed solvent and adds 0.1g polyvinylpyrrolidones point
Powder, 0.8g CaTiO3Slurry 3 is made in perovskite electrolyte inorganic filler.And it is made three kinds of slurries is agitated at room temperature
Electrostatic spinning liquid is obtained respectively after 10h, ultrasonic 1h.
Step 203, step 202 gained electrostatic spinning is subjected to electrostatic spinning with liquid, on being covered with the receiver of aluminium foil
Positive plate afterwards, voltage is 25kV, spout and receiver distance 10cm, spinning solution and environment temperature 25 between spout and receiver
DEG C, spout injection speed 0.2mL/h, spout movement speed 15mm/s.
When step 202 gained electrostatic spinning is carried out electrostatic spinning with liquid, born on the receiver for be covered with copper foil
Pole piece, voltage is 20kV, spout and 25 DEG C of receiver distance 5cm, spinning solution and environment temperature, spout note between spout and receiver
Firing rate degree 0.1mL/h, spout movement speed 30mm/s.
Step 202 gained electrostatic spinning is subjected to electrostatic spinning with liquid, is received on the receiver for be covered with negative plate
Rice fibre electrolyte film, voltage is 20kV, spout and receiver distance 10cm, spinning solution and environment temperature between spout and receiver
25 DEG C, spout injection speed 0.2mL/h, spout movement speed 30mm/s.
Step 204：Positive plate, negative plate, the nanofiber dielectric film that step 203 is obtained, 60 DEG C in drying box
Dry 5h, button cell battery core is made after then being combined with sequence shown in FIG. 1, before polymer dielectric prepared by step 1
Body is driven with being allowed to just flood nano-fiber film and positive plate, negative plate completely in syringe filling road battery core, in argon gas ring
Under border, the microwave power for applying 300W in microwave reactor causes polymerization 120s, obtains battery core.
Step 205：The made battery core of step 204 is cut into after the disk of diameter 18mm at normal temperatures through 10kgf/cm2's
Compression moulding under pressure is assembled button cell and is sealed and obtained after cooling with the sequence of anode cover, battery core, gasket, shrapnel, negative electrode casing
Obtain addition monomers battery.
Embodiment three
Step 301, by 80g AN, 5g LiPF6、5g LiBF4, 1g repefrals plasticiser, 0.05g
FeCl3Initiator is dissolved in 10ml ethylene carbonates, polymer dielectric presoma is made in 10ml dimethyl carbonate mixed solvents；?
The microwave power for applying 500W in microwave reactor causes polymerization 100s, and polymer dielectric is made.
Step 302, it is dissolved in 4ml N-Methyl pyrrolidones by the made polymer dielectric 0.2g of step 301 and dispersion is made
Liquid；Positive electrode active materials 0.8g lithium manganese phosphates, conductive agent 0.1g acetylene blacks；Negative electrode active material selects 0.8g natural stones
Slurry 1 and slurry 2 is respectively prepared according to the method for embodiment one in ink, conductive agent 0.1g acetylene blacks.Described in 0.2g step 1
Polymer dielectric is dissolved in 2ml ethylene carbonates and 2ml dimethyl carbonates in the mixed solvent and adds 0.1g polyvinylpyrrolidines
Ketone dispersant, 0.8g CaTiO3Slurry 3 is made in perovskite electrolyte inorganic filler.And made three kinds of slurries are passed through at room temperature
10h is stirred, electrostatic spinning liquid is obtained respectively after ultrasonic 1h.
Step 303, step 302 gained electrostatic spinning is subjected to electrostatic spinning with liquid, on being covered with the receiver of aluminium foil
Positive plate afterwards, voltage is 25kV, spout and receiver distance 10cm, spinning solution and environment temperature 25 between spout and receiver
DEG C, spout injection speed 0.2mL/h, spout movement speed 15mm/s.
When step 302 gained electrostatic spinning is carried out electrostatic spinning with liquid, born on the receiver for be covered with copper foil
Pole piece, voltage is 20kV, spout and 25 DEG C of receiver distance 5cm, spinning solution and environment temperature, spout note between spout and receiver
Firing rate degree 0.1mL/h, spout movement speed 30mm/s.
Step 302 gained electrostatic spinning is subjected to electrostatic spinning with liquid, is received on the receiver for be covered with negative plate
Rice fibre electrolyte film, voltage is 20kV, spout and receiver distance 10cm, spinning solution and environment temperature between spout and receiver
25 DEG C, spout injection speed 0.2mL/h, spout movement speed 30mm/s.
Step 304, positive plate, negative plate, nanofiber dielectric film step 303 obtained, 60 DEG C in drying box
Dry 5h, then button cell battery core is made after attached sequence combination shown in FIG. 1, polymer dielectric prepared by step 1
Presoma in syringe filling road battery core with being allowed to just flood nano-fiber film and positive plate, negative plate completely, in argon gas
Under environment, the microwave power for applying 500W in microwave reactor causes polymerization 100s, obtains battery core.
Step 305：The made battery core of step 304 is cut into after the disk of diameter 18mm at normal temperatures through 10kgf/cm2's
Compression moulding under pressure is assembled button cell and is sealed and obtained after cooling with the sequence of anode cover, battery core, gasket, shrapnel, negative electrode casing
Obtain addition monomers battery.
Example IV
Step 401, by 20g EO, 5g LiClO4, 3g vinyltriethoxysilane fire retardant, two isobutyl of 0.01g azos
Nitrile initiator is dissolved in 10ml ethylene carbonates, polymer dielectric presoma is made in 10ml dimethyl carbonate mixed solvents；Micro-
The microwave power for applying 300W in wave reactor causes polyase 13 00s, and polymer dielectric is made.
Step 402, it is dissolved in 4ml N-Methyl pyrrolidones by the made polymer dielectric 0.8g of step 401 and dispersion is made
Liquid；Positive electrode active materials 0.8g LiFePO4s, conductive agent 0.1g acetylene blacks；Negative electrode active material selects 0.7g hard carbons, leads
Slurry 1 and slurry 2 is respectively prepared according to the method for embodiment one in electric agent 0.15g acetylene blacks.It will gather described in 0.45g step 1
Polymer electrolyte is dissolved in 2ml ethylene carbonates and 2ml dimethyl carbonates in the mixed solvent and adds 0.05g polyvinylpyrrolidones
Slurry 3 is made in dispersant, 0.5g LLZO perovskite electrolyte inorganic fillers.And it is made three kinds of slurries is agitated at room temperature
Electrostatic spinning liquid 1,2,3 is obtained after 10h, ultrasonic 1h respectively.
Step 403, step 402 gained electrostatic spinning is subjected to electrostatic spinning with liquid, on being covered with the receiver of aluminium foil
Positive plate afterwards, voltage is 25kV, spout and receiver distance 10cm, spinning solution and environment temperature 25 between spout and receiver
DEG C, spout injection speed 0.2mL/h, spout movement speed 15mm/s.
When step 402 gained electrostatic spinning is carried out electrostatic spinning with liquid, born on the receiver for be covered with copper foil
Pole piece, voltage is 20kV, spout and 25 DEG C of receiver distance 5cm, spinning solution and environment temperature, spout note between spout and receiver
Firing rate degree 0.1mL/h, spout movement speed 30mm/s.
Step 402 gained electrostatic spinning is subjected to electrostatic spinning with liquid, is received on the receiver for be covered with negative plate
Rice fibre electrolyte film, voltage is 20kV, spout and receiver distance 10cm, spinning solution and environment temperature between spout and receiver
25 DEG C, spout injection speed 0.2mL/h, spout movement speed 30mm/s.
Step 404：Positive plate, negative plate, the nanofiber dielectric film that step 403 is obtained, 60 DEG C in drying box
Dry 5h, then button cell battery core is made after attached sequence combination shown in FIG. 1, polymer dielectric prepared by step 1
Presoma in syringe filling road battery core with being allowed to just flood nano-fiber film and positive plate, negative plate completely, in argon gas
Under environment, the microwave power for applying 300W in microwave reactor causes polyase 13 00s, obtains battery core.
Step 405：The made battery core of step 404 is cut into after the disk of diameter 18mm at 40 DEG C through 10kgf/cm2's
Compression moulding under pressure is assembled button cell and is sealed and obtained after cooling with the sequence of anode cover, battery core, gasket, shrapnel, negative electrode casing
Obtain addition monomers battery.
Embodiment five
Step 501, by 40g EO, 40g MMA, 20g LiPF6, 1g repefrals plasticiser, 0.04g azos
Bis-isobutyronitrile initiator is dissolved in 10ml ethylene carbonates, polymer dielectric forerunner is made in 10ml dimethyl carbonate mixed solvents
Body；5min is reacted in the case where UV cure lamp is with the power illumination of 30W, polymer dielectric is made.
Step 502, it is dissolved in 4ml N-Methyl pyrrolidones by the made polymer dielectric 0.4g of step 501 and dispersion is made
Liquid；Positive electrode active materials 0.8g LiFePO4s, conductive agent 0.1g acetylene blacks；Negative electrode active material selects 0.8g natural stones
Slurry 1 and slurry 2 is respectively prepared according to the method for embodiment one in ink, conductive agent 0.1g acetylene blacks.Described in 0.2g step 1
Polymer dielectric is dissolved in 2ml ethylene carbonates and 2ml dimethyl carbonates in the mixed solvent and adds 0.1g polyvinylpyrrolidines
Ketone dispersant, 0.8g CaTiO3Slurry 3 is made in perovskite electrolyte inorganic filler.And made three kinds of slurries are passed through at room temperature
10h is stirred, electrostatic spinning liquid 1,2,3 is obtained respectively after ultrasonic 1h.
Step 53, step 502 gained electrostatic spinning is subjected to electrostatic spinning with liquid, on the receiver for be covered with aluminium foil after
Positive plate, voltage is 25kV between spout and receiver, spout and 25 DEG C of receiver distance 10cm, spinning solution and environment temperature,
Spout injection speed 0.2mL/h, spout movement speed 15mm/s.
When step 502 gained electrostatic spinning is carried out electrostatic spinning with liquid, born on the receiver for be covered with copper foil
Pole piece, voltage is 20kV, spout and 25 DEG C of receiver distance 5cm, spinning solution and environment temperature, spout note between spout and receiver
Firing rate degree 0.1mL/h, spout movement speed 30mm/s.
Step 502 gained electrostatic spinning is subjected to electrostatic spinning with liquid, is received on the receiver for be covered with negative plate
Rice fibre electrolyte film, voltage is 20kV, spout and receiver distance 10cm, spinning solution and environment temperature between spout and receiver
25 DEG C, spout injection speed 0.2mL/h, spout movement speed 30mm/s.
Step 504：Positive plate, negative plate, the nanofiber dielectric film that step 503 is obtained, 60 DEG C in drying box
Dry 5h, then button cell battery core is made after attached sequence combination shown in Fig. 4, polymer dielectric prepared by step 1
Presoma in syringe filling road battery core with being allowed to just flood nano-fiber film and positive plate, negative plate completely, in argon gas
Under environment, the microwave power for applying 300W in microwave reactor causes polymerization 120s, obtains battery core.
Step 505：The made battery core of step 504 is cut into after the disk of diameter 18mm at 40 DEG C through 10kgf/cm2's
Compression moulding under pressure is assembled button cell and is sealed and obtained after cooling with the sequence of anode cover, battery core, gasket, shrapnel, negative electrode casing
Obtain addition monomers battery.
Fig. 2 is the SEM figures of the electrospun fibers film prepared by slurry 1 in the embodiment of the present invention one；As shown in Fig. 2,
Round pearl is electrode active material in figure, it is shown that positive active material wherein be uniformly distributed and it is a large amount of empty
Gap, this structure provide space to the filling of polymer dielectric presoma, are also provided largely for the migration of lithium ion
Channel.
Table 1 is the embodiment of the present invention one, and embodiment two, embodiment three, example IV and embodiment object carry out electrochemistry survey
The result of examination and cycle performance test.
One electro-chemical test of table and cycle performance test result table
As shown in Table 1, for embodiment one, anode specific capacity as shown in Figure 3 has bright up to 141.3mAh/g
Charge and discharge platform voltage that is aobvious and stablizing；Capacity retention ratio reaches 97.3% after being recycled at 100 times shown in Fig. 4.As a result it shows
Have according to the battery prepared by a kind of production method of polymer matrix all-solid lithium-ion battery provided by the present invention good
Cyclical stability, and can be applied to a variety of solid electrolytes and electrode active material and prepare all-solid lithium-ion battery.
In conclusion the embodiment of the present invention provides a kind of preparation method of all-solid lithium-ion battery, including：By mass ratio
For the polymer monomer of 10-30%, the lithium salts of 1-10%, the initiator of 0.001-5%, the additive of 0.001-5%, which is dissolved in, to be had
In solvent, it is prepared into polymer dielectric；Polymer-positive-active the material that will be sequentially prepared by the polymer dielectric
Material, polymer-negative electrode active material and polymer dielectric-inorganic filler mixed, be stirred at a set temperature with
And ultrasonic vibration, obtain electrostatic spinning liquid；The electrostatic spinning is subjected to electrostatic spinning with liquid, is being covered with connecing for collector
It receives and prepares positive plate and negative plate respectively on device, made on the receiver for being covered with the negative plate or the positive plate
Standby fiber membrane；By the positive plate, the fiber membrane and the negative plate are sequentially overlapped and are prepared into battery core, by the battery core
It through hot pressing, seals, all-solid lithium-ion battery is made after shaping and degasification in chemical conversion.The production method, making step is simple, system
Make at low cost.The battery consistency prepared by this method is good, and high mechanical strength, security performance are high, hold in charge and discharge process
Amount decaying is few, can be applied to demand large capacity, high security, high-power use occasion.
Although preferred embodiments of the present invention have been described, it is created once a person skilled in the art knows basic
Property concept, then additional changes and modifications may be made to these embodiments.So it includes excellent that the following claims are intended to be interpreted as
It selects embodiment and falls into all change and modification of the scope of the invention.
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by those skilled in the art
God and range.In this way, if these modifications and changes of the present invention belongs to the range of the claims in the present invention and its equivalent technologies
Within, then the present invention is also intended to include these modifications and variations.
Claims (7)
1. a kind of preparation method of all-solid lithium-ion battery, which is characterized in that including：
By mass ratio be 10-30% polymer monomer, the lithium salts of 1-10%, the initiator of 0.001-5%, 0.001-5%'s
Additive is dissolved in organic solvent, is prepared into polymer dielectric；
Polymer-the positive electrode active materials that will be sequentially prepared by the polymer dielectric, polymer-negative electrode active material and
Polymer dielectric-inorganic filler is mixed, and is stirred at a set temperature and ultrasonic vibration, and electrostatic spinning use is obtained
Liquid；
The electrostatic spinning is subjected to electrostatic spinning with liquid, be prepared into respectively on the receiver for be covered with collector positive plate and
Negative plate prepares fiber membrane on the receiver for being covered with the negative plate or the positive plate；
By the positive plate, the fiber membrane and the negative plate are sequentially overlapped, filled polymer electrolyte precursor simultaneously
It is prepared into battery core after causing polymerization, by the battery core through hot pressing, is sealed, all solid state lithium ion is made after shaping and degasification in chemical conversion
Battery.
2. the method as described in claim 1, which is characterized in that described by the polymer monomer that mass ratio is 10-30%, 1-
The additive of 10% lithium salts, the initiator of 0.001-5%, 0.001-5% is dissolved in organic solvent, is prepared into polymer electrolytic
Matter specifically includes：
By mass ratio be 10-30% polymer monomer, the lithium salts of 1-10%, the initiator of 0.001-5%, 0.001-5%'s
Additive is dissolved in organic solvent, is prepared into polymer dielectric presoma；Made polymer dielectric presoma is aggregated
Initiation is prepared into the polymer dielectric；The polymerization initiation includes the thermal initiation of 10-200 DEG C of temperature；Or cause power
The microwave of 0-1000W causes；Or emission wavelength 250-400nm, power 10-2000W's is light-initiated；Or voltage 0-10V, electricity
The electricity for flowing 1-1000mA causes.
3. method as claimed in claim 2, which is characterized in that described by the positive plate, the fiber membrane and described negative
Pole piece, which is sequentially overlapped, is prepared into battery core, specifically includes：
Be superimposed according to the order of positive plate, fiber membrane and negative plate, the wherein collector of positive plate and negative plate towards outside,
Fiber membrane blocks being in direct contact for positive plate and negative plate completely；The polymer dielectric presoma is filled with syringe
To between the positive plate, fiber membrane and the negative plate and polymer dielectric presoma being made to flood positive plate, fibre completely
Film and negative plate are tieed up, battery core is prepared by polymerizeing to cause.
4. the method as described in claim 1, which is characterized in that it is described will be sequentially prepared by the polymer dielectric it is poly-
Object-positive electrode active materials are closed also to wrap before polymer-negative electrode active material and polymer dielectric-inorganic filler are mixed
It includes：
By conducting polymer, the polymer dielectric is dissolved in the organic solvent and is prepared into respectively with positive electrode, mixing
Polymer-positive electrode active materials；
By conducting polymer, the polymer dielectric is dissolved in the organic solvent and is prepared into respectively with negative material, mixing
Polymer-negative electrode active material；
The polymer dielectric is dissolved in the organic solvent and to be prepared by mixing into polymer dielectric-with inorganic filler inorganic
Filler；
It is described to be stirred in the case where setting whipping temp and ultrasonic vibration, electrostatic spinning liquid is obtained, is specifically included：
At room temperature by the polymer-positive electrode active materials, the conducting polymer-negative electrode active material and the polymer
After electrolyte-inorganic filler stirring 1-10h, by ultrasonic vibration, electrostatic spinning liquid is obtained；The setting whipping temp 10-
50 DEG C, the ultrasonic vibration time 0.5-5h.
5. method as claimed in claim 4, which is characterized in that the conducting polymer be polythiophene, polypyrrole, polyacetylene,
One kind or and several in the derivative of polyaniline and these four conducting polymers；
The positive electrode includes LiFePO4, lithium manganese phosphate, cobalt acid lithium, LiMn2O4, lithium nickelate, nickel-cobalt-manganese ternary, nickel cobalt aluminium
One or more combinations in ternary, nickel manganese binary material；
The negative material includes natural graphite, artificial graphite, silica-base material, hard carbon, metal complex frame clsss negative material
In one or more combinations；
The inorganic filler is Ca-Ti ore type, NASICON types, LISICON types, carbuncle type metal oxide, metal sulfide
In one kind.
6. the method as described in claim 1, which is characterized in that it is described that the electrostatic spinning is subjected to electrostatic spinning with liquid,
It is covered on the receiver of collector and prepares positive plate and negative plate respectively, be covered with the negative plate or the positive plate
The receiver on prepare fiber membrane, specifically include：
The electrostatic spinning is subjected to electrostatic spinning with liquid, is being covered with the receiver that thickness is the aluminium foil between 100nm-5 μm
Upper acquisition positive plate, wherein electrostatic spinning voltage is 25kV, 25 DEG C, injection speed 0.2mL/h of electrostatic spinning temperature, spout shifting
Dynamic speed 15mm/s；
The electrostatic spinning is subjected to electrostatic spinning with liquid, is being covered with the receiver that thickness is the copper foil between 100nm-5 μm
Upper acquisition negative plate, wherein electrostatic spinning voltage 20kV, 25 DEG C, injection speed 0.1mL/h of electrostatic spinning temperature, spout movement
Speed 30mm/s；
The electrostatic spinning is subjected to electrostatic spinning with liquid, it is 200nm-50 that thickness is obtained on the receiver for be covered with negative plate
Fiber membrane between μm, wherein electrostatic spinning voltage 20kV, 25 DEG C, injection speed 0.2mL/h of electrostatic spinning temperature, spout
Movement speed 30mm/s.
7. the method as described in claim 1, which is characterized in that the polymer monomer includes following substance and its derivative
It is one or more：EO,MMA,VDF,VC,PC,BA,AN,TMV,PO；
The lithium salt material includes LiPF6、LiBOB、LiBF4、LiTFSI、LiClO4At least one of；
The initiator is at least one of organic peroxide class, azo, redox type free base initiator；
The additive is one or more combinations in plasticiser, surfactant, fire retardant, dispersant；
The organic solvent is ethyl alcohol, acetone, isopropanol, petroleum ether, acetonitrile, carbonates, amides, N- crassitudes
Ketone, dimethyl sulfoxide (DMSO), N- ethyl pyrrolidones, one kind in triethylamine or combination.
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| JP2018246339A JP2019204765A (en) | 2018-05-23 | 2018-12-27 | Method for manufacturing all-solid lithium ion battery |
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