CN110323493A - A kind of anode pole piece and the compounded plate of polymer dielectric film and preparation method thereof - Google Patents
A kind of anode pole piece and the compounded plate of polymer dielectric film and preparation method thereof Download PDFInfo
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- CN110323493A CN110323493A CN201810287373.XA CN201810287373A CN110323493A CN 110323493 A CN110323493 A CN 110323493A CN 201810287373 A CN201810287373 A CN 201810287373A CN 110323493 A CN110323493 A CN 110323493A
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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
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/0071—Oxides
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- 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
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- 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 present invention provides the preparation methods of anode pole piece and the compounded plate of polymer dielectric film, comprising: (1) by positive electrode active materials and ceramic base solid electrolyte ball-milling treatment；(2) under heating, polymeric binder is dissolved in organic solvent, lithium salts is added, stirring makes it completely dissolved；(3) solution in (2) is taken, ceramic base solid electrolyte is added, after stirring in a mold, polymer dielectric film is made in solvent evaporated；(4) solution obtained in (2) is taken, positive electrode active materials and conductive additive in (1) are added, are coated on aluminium foil after stirring, is dried, anode pole piece is made；(5) it is combined after anode pole piece tabletting with the polymer dielectric film in (3), tabletting, melt process obtains compounded plate.This method can improve the compatibility of positive plate and dielectric film, increase the solid solid interface contact of solid state battery, reduce impedance；The coulombic efficiency for effectively improving battery gives full play to the advantage of electrode material.
Description
Technical field
The present invention relates to field of lithium ion battery, in particular to a kind of preparation method of solid state battery positive electrode pole piece with
And application.
Background technique
Lithium ion battery is the highest electrochemical energy storage system of energy density for having obtained application.With lithium ion battery
Power vehicle and it is extensive in terms of application, market proposes higher want to its energy density and security performance
It asks.
For energy density angle, the capacity of graphite cathode be can achieve in existing lithium ion battery negative material
300mAhg-1 or more, the silicon-carbon composite cathode with higher capacity have also started small range application；And positive electrode is difficult to dash forward
Broken 200mAhg-1, becomes the principal element of limiting lithium ion cell energy density promotion.From the composition of lithium ion battery,
Positive electrode accounts for significant proportion, about 3-4 times of negative electrode material.
As it can be seen that the performance of positive electrode directly affects the quality of battery performance, develop higher energy density lithium ion electricity
Pond positive electrode is the only way which must be passed of lithium ion battery development.
Currently, research is more high voltage cobalt acid lithium, high-voltage spinel phase, lithium-rich manganese base material and nickelic ternary
System etc..In addition to positive electrode performance itself, excellent anode pole piece preparation method is also one of the probing direction of battery manufacturer.
In addition, all solid state lithium metal battery is due to its high ratio energy with the high request that market proposes lithium ion battery
Amount and high security performance receive significant attention.But at present for, all-solid-state battery is faced with examining for very severe
It tests, is difficult to realize on solid state battery including its excessive interface impedance, fast charge, preparation process is immature and high expensive
Deng.
Wherein, solid solid interface problem is the current most important thing, the interface between solid electrolyte and electrode material be it is solid-
Solid fraction state, therefore effectively contacting between electrode and electrolyte is weaker, it is slower that ion transmits dynamics in solid matter, fast charge
It is difficult to realize；Also, current solid state battery internal resistance is larger, will cause irreversible energy loss during the charging process；Solid-state
Battery preparation technique is not mature enough, and cost is high etc..
The present inventor improves the prior art due to the above reasons, develops a kind of positive electrode of solid state battery
Pole piece and its preparation method and application.
Summary of the invention
To solve the above-mentioned problems, present inventor has performed sharp studies, as a result, it has been found that: it is with polymer electrolyte matrix
Binder, and the technique of high-temperature fusion processing is carried out to positive plate and solid electrolyte, solid-state can be solved to a certain extent
Solid solid interface insufficient contact and impedance problems of too in battery, the cladding of ceramic base solid electrolyte is not only in positive plate
Help to improve the chemical property of positive electrode, moreover it is possible to improve the compatibility between anode and solid electrolyte piece；In addition, lithium
The addition of salt can also effectively improve the coulombic efficiency of battery, give full play to the advantage of electrode material, so as to complete the present invention.
The purpose of the present invention is to provide following aspect:
In a first aspect, the present invention provides a kind of preparation method of the compounded plate of anode pole piece and polymer dielectric film, it should
Method includes:
Positive electrode active materials and ceramic base solid electrolyte are carried out ball-milling treatment by step (1), make positive electrode active materials table
Bread is covered with ceramic base solid electrolyte；
Under step (2) heating, polymeric binder is dissolved in organic solvent, lithium salts is added, stirring keeps it completely molten
Solution；
Step (3) takes solution obtained in step (2), and ceramic base solid electrolyte is added and is poured over after mixing evenly
In mold, polymer dielectric film is made in solvent evaporated；
Step (4) takes solution obtained in step (2), and surface obtained in step (1) is added and is coated with ceramic base solid-state
The positive active material and conductive additive of electrolyte, stirring are slurried, are coated on aluminium foil, and anode pole piece is made in drying；
Step (5), by after anode pole piece tabletting obtained in step (4), with polymer dielectric obtained in step (3)
Film combination, tabletting again, melt process obtain the compounded plate of anode pole piece and polymer dielectric film.
The present invention also provides the compounded plate of a kind of anode pole piece prepared by the above method and polymer dielectric film, institutes
Stating compounded plate can be used as anode pole piece and dielectric film for solid state battery.
A kind of anode pole piece and the compounded plate of polymer dielectric film for there is provided according to the present invention and preparation method thereof, have
Below the utility model has the advantages that
(1) using polymer dielectric as binder, and the work of high-temperature fusion processing is carried out to positive plate and solid electrolyte
Skill can solve solid solid interface insufficient contact and impedance problems of too in solid state battery to a certain extent；
(2) cladding of ceramic base solid electrolyte not only facilitates the chemical property for improving positive electrode in positive plate,
The compatibility between anode and solid electrolyte piece can also be improved；In addition, the addition of lithium salts can also effectively improve the library of battery
Human relations efficiency gives full play to the advantage of electrode material.
Detailed description of the invention
Fig. 1 shows the ac impedance spectroscopy of polymer dielectric film obtained in embodiment 1；
Fig. 2 shows the maps of the ionic conductivity of polymer dielectric film obtained in embodiment 1；
Fig. 3 shows the map of the electrochemical window of polymer dielectric film obtained in embodiment 1；
Fig. 4 shows the charge-discharge test map of LFP/PEO-LiTFSI/Li solid state battery obtained in embodiment 1；
Fig. 5 shows the charge-discharge test map of LCO/PAN-LiTFSI/Li solid state battery obtained in embodiment 2；
Fig. 6 shows the SEM electromicroscopic photograph that the cobalt acid lithium of LATP is coated in embodiment 2.
Specific embodiment
Present invention will now be described in detail, and the features and advantages of the invention will become more with these explanations
It is clear, clear.
Dedicated word " exemplary " means " being used as example, embodiment or illustrative " herein.Here as " exemplary "
Illustrated any embodiment should not necessarily be construed as preferred or advantageous over other embodiments.Although each of embodiment is shown in the attached drawings
In terms of kind, but unless otherwise indicated, it is not necessary to attached drawing drawn to scale.
In the description of the present invention, it should be noted that term " first ", " second ", " third " and " the 4th " are only used for
Purpose is described, relative importance is not understood to indicate or imply.
The present invention described below.
The present invention provides the preparation method of a kind of anode pole piece and the compounded plate of polymer dielectric film, the method packets
Include following steps:
Step (1), positive electrode active materials and ceramic base solid electrolyte carry out high-energy ball milling, make surface of positive electrode active material
It is coated with ceramic base solid electrolyte, it is spare；
Preferably, it includes cobalt acid lithium (LCO), LiFePO4 (LFP), tertiary cathode that the positive electrode active materials, which are selected from,
(NCM/NCA), LiMn2O4 (LMO), spinel nickel LiMn2O4 (LNMO) and one of lithium-rich manganese-based or a variety of；Preferably phosphoric acid
Iron lithium or cobalt acid lithium；
Preferably, the ceramic base solid electrolyte is titanium phosphate aluminium lithium (LATP), phosphoric acid germanium aluminium lithium (LAGP), lithium lanthanum zirconium
One of oxygen (LLZO) is a variety of, preferably LATP or LLZO；
The mass ratio of the positive electrode active materials and ceramic base solid electrolyte is 100:(20-0.1), preferably 100:
(5-0.5), more preferably 100:(2.5-0.5), such as 100:2,100:1.
The revolving speed of high energy ball mill is 200-400r/h, preferably 350r/h；Ball-milling treatment 5-10h, preferably 5-8h.
By ball milling, positive electrode active materials and the partial size of ceramic base solid electrolyte can be made to further decrease, specific surface
Product significantly improves；At the same time it can also equably coat upper one layer of solid electrolyte membrane in surface of positive electrode active material, facilitate just
The raising of pole chemical property and compatible raising between electrolyte sheet.
Under step (2), heating, polymeric binder is dissolved in organic solvent, is slow added into lithium salts, stirring makes it
It is completely dissolved；
Preferably, the polymeric binder is polyethylene glycol oxide (PEO), Kynoar (PVDF-HFP), polypropylene
One of nitrile (PAN) or polymethyl methacrylate (PMMA) are a variety of.
More preferable polymeric binder is the PEO that molecular weight is 10-100 ten thousand or the PAN that molecular weight is 2.5-20 ten thousand.
The organic solvent is dimethylformamide (DMF), dimethyl sulfoxide (DMSO), tetrahydrofuran or isopropyl acetate
One of or it is a variety of, it is preferable to use dimethylformamide or dimethyl sulfoxide are solvent.
The concentration of preferred polymers binder in organic solvent be 0.1-10g/ml, more preferably 0.15-5g/ml, most
It is well 0.16-2g/ml, such as 0.2g/ml, 0.5g/ml, 1g/ml or 1.5g/ml.
Lithium in electrode material will cause the irreversible loss of lithium in battery first charge-discharge, by into organic solution
Lithium salts is added, the loss of lithium can be cut down.
Preferably, the lithium salts being added into organic solution is lithium hexafluoro phosphate (LiPF6), lithium perchlorate (LiClO4), double three
Fluoromethane sulfimide lithium (LiTFSI), double fluorine sulfimide lithiums (LiFSI), lithium sulfate (Li2SO4), lithium iodide (LiI) or nitre
Sour lithium (LiNO3) one of or a variety of, preferably LiTFSI or LiClO4。
Preferably, the mole dosage ratio of Li ion is (10- in polymer monomer and lithium salts in the polymeric binder
20): 1, more preferably (12-18): 1, for example, 12:1,16:1.
Lithium in electrode material will cause the irreversible loss of lithium in battery first charge-discharge, by the way that the lithium is added
Salt can reduce and cut down reduction of the irreversible loss of lithium to battery coulombic efficiency, can effectively improve the coulomb of battery
Efficiency gives full play to the advantage of electrode material.
Step (3) takes solution in step (2), and ceramic base solid electrolyte is added and is poured over mold after mixing evenly
In, polymer dielectric film is made in solvent evaporated；
It is preferred that the amount ratio (g:ml) of the ceramic base solid electrolyte and solution obtained in (2) the step of taking-up is
0.05%-1%, preferably 0.05%-0.5%, more preferably 0.1%-0.3%, such as 0.2%.
Wherein, the partial size of the ceramic base solid electrolyte is 200nm-5 μm；Preferably 200nm-1 μm.
In the solution after mixing evenly by ceramic base solid electrolyte, the slurry of polymer dielectric film is made.
Polymeric binder primarily serves plasticizer effect, improves the plasticity of ceramic base solid electrolyte membrane；In addition, polymerization
Object binder can also improve the ionic conductivity and lithium ionic mobility of ceramic base solid electrolyte membrane.
It is preferable to use molds to prepare polymer dielectric film, has the reservoir of setting volume and shape in the mold,
The solution or slurry of setting volume can be accommodated.
Preferably, the slurry of obtained polymer dielectric film is poured into mold, then the solvent in the slurry is evaporated, i.e.,
Solid polymer dielectric film can be obtained.
The mold does not do any restrictions, as long as when meeting receiving setting volume of liquid and being able to bear solvent evaporated
High temperature.
Preferably, the solvent in mold is evaporated using the method for heating, to prepare solid polymer dielectric film.Example
Such as, the mold for accommodating polymer dielectric film slurry is placed in baking oven, it is molten by heating the method for making solvent volatilize reduction
Agent content is evaporated substantially up to solvent, and vacuum drying oven also can be used and be dried.
More preferably during solvent evaporates, heating temperature is 50-60 degree, can fast implement being evaporated for solvent.
Step (4) takes solution obtained in step (2), is added and obtained in step (1) is coated with solid electrolyte membrane
Positive active material and conductive additive, stirring are slurried, and are coated on aluminium foil, and anode pole piece is made in drying；
Wherein, it is gentle to be selected from carbon black, Ketjen black, graphite, graphite oxide, graphene, carbon nanotube for the conductive additive
Mutually one of deposition carbon fiber or a variety of；Preferably carbon black or graphite.
Further, the mass ratio of the positive active material and conductive additive is (20-1): 1；Preferably (15-1):
1, more preferably (10-2): 1, such as 8:1,3.5:1,2:1.
The hybrid mode of the positive active material and conductive additive does not further limit, and existing skill can be used
Any one of art hybrid mode, such as ground and mixed, sieving is mixed, is stirred etc., it is preferable to use ground and mixed, in this way
Positive active material and conductive additive can be crushed while mixing, reduce positive active material and conductive addition
The partial size of agent improves the uniformity of mixing, is conducive to improve electric property.
By the mixture after positive active material and conductive additive grinding, it is added obtained molten in the step of taking out (2)
In liquid, it is uniformly mixed.
The amount ratio of solution obtained in the step of mixture and taking-up of positive active material and conductive additive (2)
(g/ml) it is (5-1): 1, preferably (3-1): 1, for example, 9:5,2:1.
Further, in step 4, the mass ratio of the positive active material and polymeric binder is (25-5): 1, it is excellent
It is selected as (15-5): 1, more preferably (10-5): 1, such as 8:1,7:1,6:1.
In solution in the step of positive active material and conductive additive are added to taking-up (2), become after mixing evenly
The slurry of pole piece of positive pole single side is coated on aluminium foil by the slurry of anode pole piece, the coating of the preferably described slurry of pole piece of positive pole
Density is 50-300mg/cm2, more preferably 150-250mg/cm2。
The aluminium foil for being coated with slurry of pole piece of positive pole dries 6-12h at 50-80 DEG C, is preferably done in vacuum drying oven
It is dry, anode pole piece is made.
Step (5), by after anode pole piece tabletting obtained in step (4), with polymer dielectric obtained in step (3)
Film combination, tabletting again, melt process obtain the compounded plate of anode pole piece and solid electrolyte.
In order to increase in step (4) the solid of polymer dielectric film obtained in anode pole piece obtained and step (3)
The two is preferably carried out compressing tablet process and melt process, so that anode pole piece and polymer dielectric film Gu Gu circle by interfacial contact
Face contact is more abundant.
Preferably, tabletting is carried out to anode pole piece obtained in step (4) first, pressure controls between 1-10Mpa；It is logical
Tabletting is crossed, so that the positive active material and conductive additive spacing in anode pole piece reduce, electric conductivity is improved；Meanwhile making
The surface for obtaining anode pole piece is more smooth, is conducive to contact with polymer dielectric film well.
It combines the anode pole piece after tabletting with polymer dielectric film obtained in step (3), tabletting again, pressure control
System is between 1-10Mpa.Tabletting anode pole piece and polymer dielectric film is combined, by the effect of pressure, improves positive pole
The problem of solid solid interface insufficient contact between piece and polymer dielectric film, improve effective contact at interface.
Further, melt process is carried out to anode pole piece and polymer dielectric film, is handled by melted by heating, it can be with
It merges the polymeric binder in anode pole piece sufficiently with the polymeric binder in polymer dielectric film, increases Gu Gu circle
The deep contact in face.Also, since in the present invention, the polymeric binder in anode pole piece and polymer dielectric film uses
Be same substance, therefore, in melt process, in the polymeric binder and polymer dielectric film in anode pole piece
After the heated thawing deformation of polymeric binder, it is easier to which mutually bonding is connected, to increase anode pole piece and polymer electrolytic
The contact area of plasma membrane improves solid solid interface contact, reduces interface impedance.
It is preferred that the temperature of the anode pole piece and polymer dielectric film melt process is 45-85 DEG C, more preferably 55-75
DEG C, such as 60 DEG C；
The time of the anode pole piece and polymer dielectric film melt process is 2-4h, such as 3h.
Using polymer electrolyte matrix as binder, and the work of high-temperature fusion processing is carried out to positive plate and solid electrolyte
Skill can solve solid solid interface insufficient contact and impedance problems of too in solid state battery to a certain extent.
In addition, the present invention also provides the groups of a kind of anode pole piece prepared using the above method and polymer dielectric film
Piece is closed, the compounded plate can be used as anode pole piece and dielectric film for solid state battery.
The compounded plate has good charging and discharging performance, and coulombic efficiency is high.
Embodiment
Embodiment 1
By LiFePO4 (LFP) and titanium phosphate aluminium lithium (LATP) according to the quality of 100:1 than ingredient after, with 350 turns/hour
Rotational speed of ball-mill carry out 6 hours ball millings, obtained surface is coated with the LiFePO4 of LATP.
The PEO that 5g molecular weight is 600,000 is weighed, is dispersed under heating in 25ml DMF solvent, is delayed after solution clarification
Slow to be added LiTFSI, stirring is to being completely dissolved.Wherein, the molar ratio of the lithium in the monomer and LiTFSI in PEO is 16:1.
The above-mentioned solution of 20ml is taken, 0.02g LATP is added thereto and is poured directly into polytetrafluoroethylene (PTFE) after mixing evenly
(PTFE) on mold, polymer dielectric film is made in solvent evaporated in 50 degree of baking ovens.
Meanwhile surface being taken to be coated with the LiFePO4 8g of LATP, carbon black 1g is added in remaining DMF solution, continues to stir
Uniform slurry is mixed, equably single side is coated in Al foil by it, dries in 80 degree of vacuum drying ovens, iron phosphate lithium electrode is made
Piece.
By iron phosphate lithium electrode piece compressing tablet process, the condition of compressing tablet process is 8Mpa.By the LiFePO4 after compressing tablet process
Electrode slice carries out tabletting, tabletting conditions 8Mpa again after combining with polymer dielectric film.
It is small that the compounded plate of polymer dielectric film and iron phosphate lithium electrode piece is placed on melt process 2 in 60 degree of baking ovens
When, it is down to room temperature (20-25 degree) naturally, obtains LFP/PEO pole piece.
LFP/PEO pole piece is directly matched with lithium metal and is assembled into LFP/PEO-LiTFSI/Li solid state battery, battery is put
It is tested after stablizing 4h in 70 degree of baking ovens.
Embodiment 2
By cobalt acid lithium (LCO) and titanium phosphate aluminium lithium (LATP) according to the quality of 100:1 than ingredient after, with 350 turns/hour
Rotational speed of ball-mill carries out 6 hours ball millings, and obtained surface is coated with the cobalt acid lithium of LATP.
The PAN that 5g molecular weight is 150,000 is weighed, is dispersed under heating in 25mlDMF solvent, is delayed after solution clarification
Slow that LiTFSI is added, PAN-LiTFSI polymer dielectric is made to being completely dissolved in stirring.Wherein, the monomer in PAN with
The molar ratio of lithium is 12:1 in LiTFSI.
The above-mentioned solution of 20ml is taken, 0.04gLATP is added thereto, after mixing evenly, is poured directly into polytetrafluoroethylene (PTFE)
(PTFE) on grinding tool, polymer dielectric film is made in 50 degree of lower solvent evaporateds.
Meanwhile surface being taken to be coated with the cobalt acid lithium 6g of LATP, carbon black 3g is added to remaining polyelectrolyte solution
In, continue to stir into uniform slurry, by it, equably single side is coated on Al foil, is dried for standby in 80 degree of baking ovens, and cobalt is made
Sour lithium electrode piece.
It will be with cobalt acid lithium electrode slice compressing tablet process, wherein the condition of compressing tablet process is 8Mpa.By the cobalt acid after compressing tablet process
Lithium electrode piece carries out tabletting, tabletting conditions 8Mpa again after combining with polymer dielectric film.
The compounded plate of polymer dielectric film and cobalt acid lithium electrode slice is placed on 60 degree of baking oven melt process 2 hours, from
So room temperature (20-25 degree) is down into LCO/PAN pole piece.
LCO/PAN pole piece is directly matched with lithium metal and is assembled into LCO/PAN-LiTFSI/Li solid state battery, battery is put
It is tested after stablizing 4h in 70 degree of baking ovens.
Experimental example
Experimental example 1
Polymer dielectric film obtained in Example 1, tests its AC impedance, test condition are as follows: 10mHz-4MHz,
Perturbation 5mV tests its AC impedance at 30 DEG C, 40 DEG C, 50 DEG C and 60 DEG C respectively.
As a result as shown in Figure 1, as shown in Figure 1, as the temperature rises, the impedance of polymer dielectric is smaller and smaller.
Experimental example 2
Polymer dielectric film obtained in Example 1, tests its ionic conductivity, test condition are as follows: 10mHz-
4MHz, perturbation 5mV
As a result as shown in Fig. 2, as shown in Figure 2, the conductivity at room temperature of the polymer dielectric film of preparation is 1.45 ×
10-4S/cm2, 60 degree of its lower ionic conductivities are 2.467 × 10-3S/cm2, which is close with liquid electrolyte,
Illustrate that the polymer dielectric film has preferable Ion transfer performance.
Experimental example 3
Polymer dielectric film obtained in Example 1, tests its electrochemical window, test condition are as follows: 10mHz-
4MHz, perturbation 5mV
As a result as shown in figure 3, from the figure 3, it may be seen that this kind of electrolyte electrochemical window is up to 5V or more at room temperature, under 70 degree
It remains to reach 5V, PEO based polyalcohol (average in 4.2V or so) than in the prior art is higher by very much, can effectively ensure that electrolysis
Matter has wider operating voltage, more positive electrodes can be matched, such as high voltage cobalt acid lithium and high-voltage spinel phase.
Experimental example 4
LFP/PEO-LiTFSI/Li solid state battery obtained in embodiment 1 is subjected to charge-discharge test, voltage range is
2.5-3.8V, size of current 0.2C.
Test results are shown in figure 4, and first week charge specific capacity is 152mAhg-1, first week reversible capacity is 151.5mAhg-1,
First week coulombic efficiency is 99.8%, and 20 weeks circulation conservation rates are up to 95.65%.
Experimental example 5
LCO/PAN-LiTFSI/Li solid state battery obtained in embodiment 2 is subjected to charge-discharge test, voltage range is
3.0-4.2V, size of current 0.1C.
Test results are shown in figure 5, and first week charge specific capacity is 139.1mAhg-1, first week reversible capacity is 135.2mAhg-1, first week coulombic efficiency is 97.38%, and 20 weeks circulation conservation rates are up to 90.02%.
Experimental example 6
The cobalt acid lithium that LATP is coated with made from embodiment 2 is subjected to the observation of SEM Electronic Speculum, as shown in fig. 6, by ceramic base
Cobalt acid lithium particle surface has one layer thicker of electrolyte clad after solid electrolyte cladding, which facilitates material electrification
Learn the promotion of performance.
It is described the invention in detail above in conjunction with detailed description and exemplary example, but these explanations are simultaneously
It is not considered as limiting the invention.It will be appreciated by those skilled in the art that without departing from the spirit and scope of the invention,
Can be with various equivalent substitutions, modifications or improvements are made to the technical scheme of the invention and its embodiments, these each fall within the present invention
In the range of.Scope of protection of the present invention is subject to the appended claims.
Claims (10)
1. a kind of preparation method of the compounded plate of anode pole piece and polymer dielectric film, which is characterized in that this method comprises:
Positive electrode active materials and ceramic base solid electrolyte are carried out ball-milling treatment by step (1), make surface of positive electrode active material packet
It is covered with ceramic base solid electrolyte；
Under step (2), heating, polymeric binder is dissolved in organic solvent, lithium salts is added, stirring makes it completely dissolved；
Step (3) takes solution obtained in step (2), and ceramic base solid electrolyte is added and is poured over mold after mixing evenly
In, polymer dielectric film is made in solvent evaporated；
Step (4) takes solution obtained in step (2), and surface obtained in step (1) is added and is coated with ceramic base solid state electrolysis
The positive active material and conductive additive of matter, stirring are slurried, are coated on aluminium foil, and anode pole piece is made in drying；
Step (5), by after anode pole piece tabletting obtained in step (4), with polymer dielectric film group obtained in step (3)
It closes, tabletting again, melt process obtains the compounded plate of anode pole piece and polymer dielectric film.
2. preparation method according to claim 1, which is characterized in that in step (1), the positive electrode active materials are selected from
It is excellent including cobalt acid lithium, LiFePO4, LiMn2O4, tertiary cathode, spinel nickel LiMn2O4 or one of lithium-rich manganese-based or a variety of
It is selected as cobalt acid lithium or LiFePO4；
The ceramic base solid electrolyte be one or more of titanium phosphate aluminium lithium, phosphoric acid germanium aluminium lithium, lithium lanthanum zirconium oxygen, preferably
Titanium phosphate aluminium lithium or lithium lanthanum zirconium oxygen.
3. preparation method according to claim 1, which is characterized in that in step (1), the positive electrode active materials and pottery
The mass ratio of porcelain base solid electrolyte is 100:(20-0.1), preferably 100:(5-0.5), more preferably 100:(2.5-0.5),
Such as 100:2 or 100:1.
4. preparation method according to claim 1, which is characterized in that in step (2), the lithium salts is hexafluorophosphoric acid
One of lithium, lithium perchlorate, double trifluoromethanesulfonimide lithiums, double fluorine sulfimide lithiums, lithium sulfate, lithium iodide or lithium nitrate
Or a variety of, preferably double trifluoromethanesulfonimide lithiums or lithium perchlorate.
5. the preparation method according to claim 4, which is characterized in that in step (2), gather in the polymeric binder
The mole dosage ratio of Li ion is (10-20): 1, more preferably (12-18): 1 in monomer adduct and lithium salts.
6. preparation method according to claim 1, which is characterized in that in step (3), the ceramic base solid electrolyte
Amount ratio with solution obtained in the step of taking out (2) is 0.05%-1%g/ml, preferably 0.05%-0.5%g/ml, more
Preferably 0.1%-0.3%g/ml, such as 0.2%g/ml.
7. preparation method according to claim 1, which is characterized in that in step (4), the positive active material with lead
The mass ratio of electric additive is (20-1): 1；Preferably (15-1): 1, more preferably (10-2): 1, such as 8:1,3.5:1,2:1.
8. preparation method according to claim 1, which is characterized in that in step (4), positive active material and conduction add
The amount ratio (g/ml) of solution obtained is (5-1): 1, preferably (3-1) in the step of adding mixture and the taking-up of agent (2): 1,
For example, 9:5,2:1.
9. preparation method according to claim 1 or 8, which is characterized in that in step (5), when compressing tablet process, pressure control
System is in 1-10Mpa, such as 8Mpa；
The temperature of the anode pole piece and polymer dielectric film melt process is 45-85 DEG C, more preferably 55-75 DEG C；
The time of the anode pole piece and polymer dielectric film melt process is 2-4h.
10. a kind of compounded plate of a kind of anode pole piece and polymer dielectric film by one of claim 1-9 preparation, described group
Closing piece can be used as anode pole piece and dielectric film for solid state battery.
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