CN108933258A - The preparation method of the all-solid lithium-ion battery of three-dimensional composition metal cathode of lithium - Google Patents
The preparation method of the all-solid lithium-ion battery of three-dimensional composition metal cathode of lithium 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
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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
- H01M4/624—Electric conductive fillers
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to electrochemical power source technical fields, are specifically related to a kind of preparation method of the all-solid lithium-ion battery of three-dimensional composition metal cathode of lithium.Lithium metal is loaded on carrier material by the chemically or physically method of electrochemical deposition or melting infiltration, three-dimensional composition metal cathode of lithium is prepared, carrier material is activated carbon fiber cloth；The preparation of PMMA-PEI base full solid state polymer electrolyte film；After obtained PMMA-PEI base full solid state polymer electrolyte film is torn from polytetrafluoroethylene (PTFE) plate surface, it is stand-by to be cut into suitably size；With LiFePO4For anode, assemble to obtain all solid state lithium ion button cell according to anode-PMMA-PEI base full solid state polymer electrolyte film-three-dimensional composition metal cathode of lithium sequence.There is the three-dimensional composition metal cathode of lithium high specific energy, coulombic efficiency height, security performance height, electrode interface to stablize, and all-solid lithium-ion battery assembling process is simple, easily controllable.
Description
Technical field
The invention belongs to electrochemical power source technical field, it is specifically related to a kind of all solid state of three-dimensional composition metal cathode of lithium
The preparation method of lithium ion battery.
Background technique
All-solid lithium-ion battery refers to all secondary using the lithium of solid-state material including positive and negative anodes, electrolyte (electrolyte)
Battery is a kind of novel solid electrolyte to grow up since the 1970s.
The working principle of solid lithium battery is communicated with the principle of liquid electrolyte lithium battery, when charging in anode
Lithium ion deintercalation from the lattice of active material is migrated by solid electrolyte to cathode, and electronics is moved by dispatch from foreign news agency road direction cathode
It moves, discharge process is just the opposite with charging process.Solid lithium battery is constructively simpler than conventional lithium ion battery, solid
Electrolyte acts as the role of diaphragm in addition to substituting the function of liquid electrolyte conducting lithium ions, it is thus eliminated that lithium battery
The hidden danger such as leakage, diaphragm heat shrinkable short circuit, greatly improve battery security and specific energy.
All-solid-state battery mainly faces following several big technical problems: interface impedance between solid electrolyte and positive and negative anodes at present
It is excessively high, solid electrolyte conductivity is relatively low, material cost preparation valuableness etc..For all-solid lithium-ion battery, solid electricity
Solution matter is crucial.Solid electrolyte needs to meet the requirement such as high ionic conductivity, good mechanical performance and chemical compatibility.Furthermore
Form well contact, reducing the important hand that interface resistance is also improvement all-solid-state battery performance for solid electrolyte and electrode material
Section.
In solid state battery system, the use of lithium metal can be improved battery energy density, but most of solid electrolyte by
Existing in valence variation element makes its easy reacts with lithium metal generate the very poor boundary layer of conductivity, and there is also reactivities
Problem.In addition, the problem of volume expansion and nonuniform deposition still remains, the physics of the soft low melting point of the matter of lithium metal itself is special
Property is also that its quick sizable application and high temperature safety bring problem.Therefore, it is necessary to ability is protected and handled to lithium metal
It uses.
Summary of the invention
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of all solid lithium of three-dimensional composition metal cathode of lithium
The preparation method of ion battery.The three-dimensional composition metal cathode of lithium has specific energy height, coulombic efficiency height, has extended cycle life, property
Energy is stablized, security performance is high, electrode interface is stablized, and the preparation process of the three-dimensional composition metal cathode of lithium is simple, while this is multiple
The specific energy that electrode material is improved using collector, save the cost is not needed in the preparation process of condensation material.It is all solid state
Lithium ion battery assembling process is simple, easily controllable.
The preparation method of the all-solid lithium-ion battery of three-dimensional composition metal cathode of lithium of the present invention, specifically include with
Lower step:
(1) preparation of three-dimensional composition metal cathode of lithium: by lithium metal by the chemistry of electrochemical deposition or melting infiltration or
Physical method loads on carrier material, three-dimensional composition metal cathode of lithium (Li-C composite material) is prepared, carrier material is
Activated carbon fiber cloth；
(2) preparation of PMMA-PEI base full solid state polymer electrolyte film；
(3) it after obtained PMMA-PEI base full solid state polymer electrolyte film being torn from polytetrafluoroethylene (PTFE) plate surface, cuts out
It is stand-by at suitably size；
(4) with LiFePO4It is compound according to anode-PMMA-PEI base full solid state polymer electrolyte film-three-dimensional for anode
The sequence of lithium anode assembles to obtain all solid state lithium ion button cell.
Wherein:
PMMA is polymethyl methacrylate, and PEI is polyethyleneimine.
Activated carbon fiber cloth grammes per square metre described in step (1) is 50-300g/m2, specific surface area 500-3000m2/ g, width
Width is 500-1400mm, with a thickness of 0.3-1mm, Kong Rongwei 0.1-6cm3/ g, average pore size 0.02-300m2/g。
Activated carbon fiber cloth grammes per square metre described in step (1) is 70-250g/m2, specific surface area 1000-2500m2/ g is thick
Degree is 0.5-1mm, Kong Rongwei 0.5-4cm3/ g, average pore size 0.2-200m2/g。
Lithium metal is either physically or chemically loaded to by electrochemical deposition, melting infiltration etc. described in step (1)
In the carrier material, further preferred electrochemical deposition method.
Electrochemical deposition described in step (1) is using carrier material activated carbon fiber cloth as cathode, and lithium metal is anode,
In 0.5-7mA/cm2Current density under, 5-30mAh/cm is deposited on activated carbon fiber cloth2Metal lithium simple substance.
Preferred current density is 0.7-5mA/cm2, deposition of the metal lithium simple substance on activated carbon fiber cloth is 7-
20mAh/cm2。
Three-dimensional composition metal cathode of lithium of the present invention, the combination electrode have specific energy height, coulombic efficiency height, circulation
The advantages that service life is long, performance is stable, security performance is high, electrode interface is stablized, key are that lithium metal and solid electricity can be overcome
The interface problem of qualitative response is solved, the generation of dendrite inhibition improves service life and the cycle performance of battery.In addition, the compound gold of the three-dimensional
The preparation process for belonging to cathode of lithium is simple, while is not needed in the preparation process of the composite material using collector, and save the cost mentions
The high specific energy of electrode material.Therefore the invention has broad application prospects.
The preparation of PMMA-PEI base full solid state polymer electrolyte film described in step (2) is specifically: by PMMA and PEI
Blending polymerization reaction generates block copolymer PMMA-PEI, and PMMA-PEI and lithium salts are dissolved into organic solvent, and nanometer is added
Filler, plasticizer, heating stirring are uniformly mixed and obtain mucus, be cast in casting film-forming on polyfluortetraethylene plate, are dried in vacuo
After obtain solid polymer electrolyte membrane.
Nano-filled object is 10~25wt%, and plasticizer is the quality that 20~70wt%, PMMA and PEI blending polymerization react
Than for 4~12:2, the molar ratio of PMMA and lithium salts is 7~12:1.
Above-mentioned nano-filled object is 10-25wt%, indicates that the quality of nano-filled object accounts for the 10- of PMMA-PEI matrix
25wt%；Plasticizer is 20~70wt%, indicates that the quality of plasticizer accounts for the 20-70wt% of PMMA-PEI matrix.
Preferred nano-filled object is 15wt%, the mass ratio that plasticizer 50wt%, PMMA and PEI blending polymerization reacts
For 8:2.
Lithium salts is LiPF6, organic solvent DMF, nano-filled object is Al2O3, plasticizer is ethylene carbonate (EC).
The heating stirring time is 4~6 hours, and vacuum drying temperature is 80~100 DEG C, and drying time is 24~48 hours.
The preparation process of PMMA-PEI base full solid state polymer electrolyte film carries out in an inert atmosphere, inert gas
For argon gas or nitrogen.
As a preferred technical solution, all solid state lithium ion electricity of three-dimensional composition metal cathode of lithium of the present invention
The preparation method in pond, specifically includes the following steps:
(1) preparation of PMMA-PEI block copolymer: under the protection of inert gas, PMMA and PEI is mixed, is dissolved in
In organic solvent, copolyreaction certain time under constant temperature conditions；
(2) preparation of PMMA-PEI base full solid state polymer electrolyte film: under the protection of inert gas, PMMA-PEI and
Lithium salts dissolves in organic solvent, and nano-filled object is added；Above-mentioned raw material are stirred, is uniformly mixed and obtains clear viscous
Liquid is cast in casting film-forming on polyfluortetraethylene plate, and the PMMA-PEI base solid polymer electrolyte is obtained after vacuum drying
Film；
(3) solid polymer electrolyte membrane obtained in step (2) is torn from polytetrafluoroethylene (PTFE) plate surface, is cut, into
The relevant electrochemical property test of row.
Wherein:
In step (1), the time of the PMMA and PEI copolyreaction is 24~48 hours；The thermostat temperature be 70~
100℃。
The invention has the following advantages:
(1) present invention makees cathode with three-dimensional composition metal cathode of lithium, it is suppressed that the growth of Li dendrite solves volume expansion and asks
Topic, meanwhile, carrier material has the advantages such as bigger serface, macropore hold and electric conductivity is good, for three-dimensional composite negative pole material
When preparation, energy density, cycle life and security performance of battery etc. can be improved.
(2) PMMA-PEI base full solid state polymer electrolyte film even compact prepared by the present invention, conductivity height, electrochemistry
Window is big, good mechanical performance, substantially meets the requirement of all-solid lithium-ion battery polymer dielectric, and commercialization at present
Liquid organic electrolyte (inflammable, volatile, thermal stability is bad etc.) compared to having preferable stability and safety.
(3) preparation process of three-dimensional composition metal cathode of lithium is simple in the present invention, does not need in preparation process using afflux
Body, save the cost improve the specific energy of electrode material；The full solid state polymer electrolyte film of preparation is due to its design letter
It is single, easily fabricated, using it is safe the advantages that have been considered as substitution traditional liquid electrolyte first choice.
(4) all-solid lithium-ion battery assembling process is simple, easily controllable.Therefore, before the present invention has wide application
Scape.
Detailed description of the invention
Fig. 1 is the conductivity variation with temperature curve that different PMMA and PEI match lower polymer dielectric film；
Fig. 2 is the conductivity of polymer dielectric film with the change curve of plasticizer EC percentage composition；
Fig. 3 is (PMMA)8-(PEI)2-LiPF6-Al2O3The cyclicity of the all-solid-state battery of (15%, w/w%) system assembling
It can curve；
Fig. 4 is (PMMA)8-(PEI)2-LiPF6-Al2O3(15%, w/w%)-EC (50%, w/w%) system assembles complete
The cycle performance curve of solid state battery.
Specific embodiment
The invention will be further described with reference to embodiments.
Comparative example 1
A kind of preparation method of the novel all-solid lithium-ion battery of three-dimensional composition metal cathode of lithium, comprising the following steps:
(1) preparation of three-dimensional composition metal cathode of lithium: carrier material used in this experiment is that activated carbon fiber cloth (is purchased from
Nantong Jin Heng Environmental Protection Technology Co., Ltd), the grammes per square metre of carbon fiber is 200 grams/m, and the specific surface area of carbon fiber is
1756m2/ g, breadth 900mm, thickness are about 0.8mm, Kong Rongwei 2.6cm3/ g, average pore size 163m2/g。
Carbon cloth is cut into the electrode slice size that diameter is Φ=19mm, the carbon cloth cut out is anhydrous with acetone-
Ethyl alcohol rinses several times, until rinsing well, drying is stand-by.
Using carrier material activated carbon fiber cloth as cathode, lithium metal is anode, in 2.0mA/cm2Current density under,
10mAh/cm is deposited on activated carbon fiber cloth2Metal lithium simple substance.
(2) preparation of PMMA-PEI base full solid state polymer electrolyte film: this experiment uses traditional solvent evaporated method system
Standby polymer dielectric film, whole preparation process carry out in the glove box full of argon gas.
It weighs 800mg PMMA and 100mg PEI and is dissolved into the DMF of 50ml and (be slowly added to, prevent that too fast cause is added
PMMA agglomeration is difficult to dissolve), ultrasonic disperse 30 minutes, under 85 DEG C of constant temperature, magnetic force heating stirring 20h obtained PMMA-
PEI copolymer solution.Then 34mg LiPF is weighed6With 135mg Al2O3It is added in mixed liquor, stirs 60min under room temperature, to
After mixing, heating stirring reacts 3h to reactant under 50 DEG C of constant temperature.The gum-like product of milky is obtained, it will
Product is coated uniformly on PTFE plate, and break away from moulds after 36h is dried under 80 DEG C of vacuum conditions, obtains smooth white in surface
The all solid state electrolyte film of color.
(3) preparation of the all-solid lithium-ion battery of three-dimensional composition metal cathode of lithium: obtained PMMA-PEI base is entirely solid
After state polymer dielectric film is torn from polytetrafluoroethylene (PTFE) plate surface, it is cut into suitably sized stand-by.It is with Li-C composite material
Cathode, LiFePO4It is electric according to anode-solid polymer electrolyte membrane-cathode sequence assembling all solid state lithium ion for anode
Pond.
In this comparative example 1, it is the chemical property of Test pmma-PEI base full solid state polymer electrolyte film, this is compared
The dielectric film prepared in example 1 is clipped between two inert electrodes (stainless steel electrode), full of argon gas glove box according to
Stainless steel substrates-solid electrolyte membrane-stainless steel substrates assembled in sequence simulated battery, and ac impedance measurement is carried out to it.It is surveyed
The frequency sweeping ranges of ac impedance spectroscopy are between 1Hz~100KHz, using low alternating voltage (10mV).
Comparative example 2
With comparative example 1 the difference is that the deposition of lithium metal, the three-dimensional combination electrode in this comparative example 2 passes through in work
8mA/cm is deposited on property carbon cloth2Lithium metal, by test, load 8mA/cm2Three-dimensional composition metal cathode of lithium have
The reversible specific capacity of 2000mA/g.
Comparative example 3
Comparative example 1 weighs 800mg PMMA the difference is that ratio when prepared by PMMA-PEI polymer blend is different
(be slowly added to, prevent from being added too fast PMMA agglomeration is caused to be difficult to dissolve) is dissolved into the DMF of 50ml with 200mg PEI, ultrasound
Disperse 30 minutes, under 85 DEG C of constant temperature, magnetic force heating stirring 20h obtains PMMA-PEI copolymer solution.Then it weighs
34mg LiPF6With 150mg Al2O3It is added in mixed liquor, stirs 60min under room temperature, after mixing to reactant, 50
DEG C constant temperature under heating stirring react 3h.The gum-like product of milky is obtained, product is coated uniformly on PTFE plate
On, break away from moulds after 36h is dried under 80 DEG C of vacuum conditions, all solid state electrolyte for obtaining the smooth white in surface is thin
Film.
Comparative example 4
From comparative example 1 the difference is that ratio when prepared by PMMA-PEI polymer blend is different, 800mg is weighed
PMMA and 300mg PEI is dissolved into the DMF of 50ml (be slowly added to, prevent from being added too fast PMMA agglomeration is caused to be difficult to dissolve),
Ultrasonic disperse 30 minutes, under 85 DEG C of constant temperature, magnetic force heating stirring 20h obtained PMMA-PEI copolymer solution.Then claim
Take 34mg LiPF6With 165mg Al2O3It is added in mixed liquor, stirs 60min under room temperature, after mixing to reactant,
Heating stirring reacts 3h under 50 DEG C of constant temperature.The gum-like product of milky is obtained, product is coated uniformly on PTFE
On plate, break away from moulds after 36h is dried under 80 DEG C of vacuum conditions, all solid state electrolyte for obtaining the smooth white in surface is thin
Film.
Embodiment 1
Plasticizer EC (ethylene carbonate) is being increased with 3 difference of comparative example, is weighing 800mg PMMA and 200mg
PEI is dissolved into the DMF of 50ml (be slowly added to, prevent from being added too fast PMMA agglomeration is caused to be difficult to dissolve), and ultrasonic disperse 30 divides
Clock, under 85 DEG C of constant temperature, magnetic force heating stirring 20h obtains PMMA-PEI copolymer solution.Then 34mg is weighed
LiPF6, 400mg EC and 150mg Al2O3It is added in mixed liquor, stirs 60min under room temperature, after mixing to reactant,
Heating stirring reacts 3h under 50 DEG C of constant temperature.The gum-like product of milky is obtained, product is coated uniformly on
On PTFE plate, break away from moulds after 36h is dried under 80 DEG C of vacuum conditions, obtains all solid state electrolysis of the smooth white in surface
Matter film.
Embodiment 2
Plasticizer EC (ethylene carbonate) is being increased with 3 difference of comparative example, is weighing 800mg PMMA and 200mg
PEI is dissolved into the DMF of 50ml (be slowly added to, prevent from being added too fast PMMA agglomeration is caused to be difficult to dissolve), and ultrasonic disperse 30 divides
Clock, under 85 DEG C of constant temperature, magnetic force heating stirring 20h obtains PMMA-PEI copolymer solution.Then 34mg is weighed
LiPF6, 500mg EC and 150mg Al2O3It is added in mixed liquor, stirs 60min under room temperature, after mixing to reactant,
Heating stirring reacts 3h under 50 DEG C of constant temperature.The gum-like product of milky is obtained, product is coated uniformly on
On PTFE plate, break away from moulds after 36h is dried under 80 DEG C of vacuum conditions, obtains all solid state electrolysis of the smooth white in surface
Matter film.
Embodiment 3
Plasticizer EC (ethylene carbonate) is being increased with 3 difference of comparative example, is weighing 800mg PMMA and 200mg
PEI is dissolved into the DMF of 50ml (be slowly added to, prevent from being added too fast PMMA agglomeration is caused to be difficult to dissolve), and ultrasonic disperse 30 divides
Clock, under 85 DEG C of constant temperature, magnetic force heating stirring 20h obtains PMMA-PEI copolymer solution.Then 34mg is weighed
LiPF6, 600mg EC and 150mg Al2O3It is added in mixed liquor, stirs 60min under room temperature, after mixing to reactant,
Heating stirring reacts 3h under 50 DEG C of constant temperature.The gum-like product of milky is obtained, product is coated uniformly on
On PTFE plate, break away from moulds after 36h is dried under 80 DEG C of vacuum conditions, obtains all solid state electrolysis of the smooth white in surface
Matter film.
The test of all-solid lithium-ion battery, comprising the following steps:
(1) the conductivity test of solid polymer electrolyte membrane: the present invention tests electricity using electrochemical AC impedance method
Conductance.It is 19mm's that the full solid state polymer electrolyte film prepared in comparative example 1-4 and embodiment 1-3 is cut into diameter respectively
Size, using Zennium electrochemical workstation test macro, using stainless steel substrates (SS) as electrode, by solid electrolyte membrane group
It dresses up SS/ dielectric film/SS and symmetrically blocks battery, carry out ac impedance measurement (EIS), amplitude 10mV, frequency 10-2~
106Hz.The conductivity of dielectric film is calculated according to the following formula.
In formula, σ is the conductivity of composite electrolyte, unit S/cm；R is the impedance for the dielectric film that EIS is tested,
Ω；L is composite electrolyte film thickness, cm；S is electrode area, cm2。
(2) test of electrochemical window: electrolyte electrochemical stability determines the operating voltage range of battery, because
This, electrochemical stability is key factor one of of the electrolyte in lithium ion battery practical application.By comparative example 1, comparative example
The full solid state polymer electrolyte film prepared in 3-4 and embodiment 1-3 is cut into the size that diameter is 19mm respectively, with stainless steel
Piece (SS) is used as electrode, and solid electrolyte membrane is assembled into SS/ dielectric film/SS and symmetrically blocks battery, different current potentials is arranged
(1~5V) carries out the testing impedance under constant potential using low alternating voltage (10mV) respectively.
(3) charge-discharge test of all-solid lithium-ion battery: by (PMMA)8-(PEI)2-LiPF6-Al2O3(15%, w/
) and (PMMA) w%8-(PEI)2-LiPF6-Al2O3The all solid state polymerization of (15%, w/w%)-EC (50%, w/w%) system preparation
Object dielectric film assembles button cell in the glove box full of argon gas respectively, using Li-C composite material as cathode, LiFePO4For
Anode assembles all solid state lithium ion button cell according to anode-solid polymer electrolyte membrane-cathode sequence.
The experimental result and discussion of comparative example 1-4 and embodiment 1-3
1, difference PMMA and PEI matches the conductivity variation with temperature curve of lower polymer dielectric film
As shown in Figure 1, the conductance for the solid polymer electrolyte membrane that in comparative example 1 and comparative example 3-4 prepared by three kinds of formulas
Rate variation with temperature situation.At room temperature, (PMMA)8-(PEI)2-LiPF6-Al2O3The solid-state polymerization of (15%, w/w%) preparation
The conductivity of object dielectric film is maximum；When temperature is 40 DEG C, (PMMA)8-(PEI)1-LiPF6-Al2O3(15%, w/w%) system
The conductivity of standby polymer dielectric film is maximum；When temperature is 60 DEG C, (PMMA)8-(PEI)2-LiPF6-Al2O3(15%,
W/w%) conductivity value of the solid polymer electrolyte membrane prepared is maximum；When temperature is 80 DEG C, (PMMA)8-(PEI)3-
LiPF6-Al2O3The conductivity value of the solid polymer electrolyte membrane of (15%, w/w%) preparation is maximum.
When temperature is lower than 60 DEG C, the conductivity of the solid polymer electrolyte membrane of PMMA:PEI=8:2 preparation is higher；When
When temperature is more than 60 DEG C, the conductivity of the solid polymer electrolyte membrane of PMMA:PEI=8:3 preparation is higher.So working as PMMA:
When PEI=8:2, the conductivity performance of full solid state polymer electrolyte film is relatively high.
2, the conductivity of polymer dielectric film with plasticizer EC percentage composition change curve
As shown in Fig. 2, (PMMA) that in embodiment 1-3 prepared by three kinds of formulas8-(PEI)2-LiPF6-Al2O3(15%, w/
W%) the change curve of the conductivity of-EC (x%, w/w%, x=40%, 50%, 60%) full solid state polymer electrolyte film.EC
Percentage composition it is different, the conductivity of film is different.With the increase of EC percentage composition, the conductivity first increases and then decreases of film, EC
When percentage composition is 50%, the conductivity of all solid state electrolyte film is maximum.
(PMMA)8-(PEI)2-LiPF6-Al2O3The all solid state electricity of (15%, w/w%)-EC (50%, w/w%) system preparation
Solve the conductivity value (7.8x10 of plasma membrane-5S/cm) it is greater than (PMMA)8-(PEI)2-LiPF6-Al2O3(15%, w/w%) system
Conductivity (the 3.9x10 of the full solid state polymer electrolyte film of preparation-4S/cm)。
3、(PMMA)8-(PEI)2-LiPF6-Al2O3The cycle performance of the all-solid-state battery of (15%, w/w%) system assembling
Curve
By (PMMA)8-(PEI)2-LiPF6-Al2O3The full solid state polymer electrolyte film of (15%, w/w%) system preparation
Button cell is assembled in the glove box full of argon gas respectively, using Li-C composite material as cathode, LiFePO4For anode, according to
Anode-solid polymer electrolyte membrane-cathode sequence assembles all solid state lithium ion button cell.In BTS battery test system
The charge-discharge test of battery is carried out, test temperature is 25 DEG C.
As shown in figure 3, (PMMA)8-(PEI)2-LiPF6-Al2O3(15%, w/w%) system preparation all-solid-state battery into
Four cycle charge-discharges are gone, capacity is not high, and the performance of battery is not special rationality.
4、(PMMA)8-(PEI)2-LiPF6-Al2O3(15%, w/w%)-EC (50%, w/w%) system assembles all solid state
The cycle performance curve of battery
By (PMMA)8-(PEI)2-LiPF6-Al2O3(15%, w/w%)-EC (50%, w/w%) system is prepared all solid state
Polymer dielectric film assembles button cell in the glove box full of argon gas respectively, using Li-C composite material as cathode,
LiFePO4For anode, all solid state lithium ion button cell is assembled according to anode-solid polymer electrolyte membrane-cathode sequence.
The charge-discharge test of battery is carried out in BTS battery test system, test temperature is 25 DEG C.
As shown in figure 4, (PMMA)8-(PEI)2-LiPF6-Al2O3The preparation of (15%, w/w%)-EC (50%, w/w%) system
All-solid-state battery carried out 30 cycle charge-discharges, capacity is relative to (PMMA)8-(PEI)2-LiPF6-Al2O3(15%, w/
W% it) is greatly improved for system, the performance of battery is opposite to get a promotion.
Claims (10)
1. a kind of preparation method of the all-solid lithium-ion battery of three-dimensional composition metal cathode of lithium, it is characterised in that: specifically include
Following steps:
(1) preparation of three-dimensional composition metal cathode of lithium: lithium metal is permeated chemically or physically by electrochemical deposition or melting
Method loads on carrier material, and three-dimensional composition metal cathode of lithium is prepared, and carrier material is activated carbon fiber cloth；
(2) preparation of PMMA-PEI base full solid state polymer electrolyte film；
(3) after obtained PMMA-PEI base full solid state polymer electrolyte film being torn from polytetrafluoroethylene (PTFE) plate surface, it is cut into conjunction
Suitable ground size is stand-by；
(4) with LiFePO4For anode, according to anode-PMMA-PEI base full solid state polymer electrolyte film-three-dimensional composition metal
The sequence of cathode of lithium assembles to obtain all-solid lithium-ion battery.
2. the preparation method of the all-solid lithium-ion battery of three-dimensional composition metal cathode of lithium according to claim 1, special
Sign is: activated carbon fiber cloth grammes per square metre described in step (1) is 50-300g/m2, specific surface area 500-3000m2/ g, breadth
For 500-1400mm, with a thickness of 0.3-1mm, Kong Rongwei 0.1-6cm3/ g, average pore size 0.02-300m2/g。
3. the preparation method of the all-solid lithium-ion battery of three-dimensional composition metal cathode of lithium according to claim 2, special
Sign is: activated carbon fiber cloth grammes per square metre described in step (1) is 70-250g/m2, specific surface area 1000-2500m2/ g is thick
Degree is 0.5-1mm, Kong Rongwei 0.5-4cm3/ g, average pore size 0.2-200m2/g。
4. the preparation method of the all-solid lithium-ion battery of three-dimensional composition metal cathode of lithium according to claim 1, special
Sign is: electrochemical deposition described in step (1) is using carrier material activated carbon fiber cloth as cathode, and lithium metal is anode,
In 0.5-7mA/cm2Current density under, 5-30mAh/cm is deposited on activated carbon fiber cloth2Metal lithium simple substance.
5. the preparation method of the all-solid lithium-ion battery of three-dimensional composition metal cathode of lithium according to claim 4, special
Sign is: current density 0.7-5mA/cm2, deposition of the metal lithium simple substance on activated carbon fiber cloth is 7-20mAh/cm2。
6. the preparation method of the all-solid lithium-ion battery of three-dimensional composition metal cathode of lithium according to claim 1, special
Sign is: the preparation of PMMA-PEI base full solid state polymer electrolyte film described in step (2) is specifically: by PMMA and PEI
Blending polymerization reaction generates block copolymer PMMA-PEI, and PMMA-PEI and lithium salts are dissolved into organic solvent, and nanometer is added
Filler, plasticizer, heating stirring are uniformly mixed and obtain mucus, be cast in casting film-forming on polyfluortetraethylene plate, are dried in vacuo
After obtain solid polymer electrolyte membrane.
7. the preparation method of the all-solid lithium-ion battery of three-dimensional composition metal cathode of lithium according to claim 6, special
Sign is: nano-filled object is 10~25wt%, and plasticizer is the quality that 20~70wt%, PMMA and PEI blending polymerization react
Than for 4~12:2, the molar ratio of PMMA and lithium salts is 7~12:1.
8. the preparation method of the all-solid lithium-ion battery of three-dimensional composition metal cathode of lithium according to claim 7, special
Sign is: nano-filled object is 15wt%, and the mass ratio that plasticizer 50wt%, PMMA and PEI blending polymerization reacts is 8:2.
9. the preparation method of the all-solid lithium-ion battery of three-dimensional composition metal cathode of lithium according to claim 6, special
Sign is: lithium salts LiPF6, organic solvent DMF, nano-filled object is Al2O3, plasticizer is ethylene carbonate.
10. the preparation method of the all-solid lithium-ion battery of three-dimensional composition metal cathode of lithium according to claim 6, special
Sign is: the heating stirring time is 4~6 hours, and vacuum drying temperature is 80~100 DEG C, and drying time is 24~48 hours.
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