CN108878960A - Solid electrolyte anode and solid state battery - Google Patents
Solid electrolyte anode and solid state battery Download PDFInfo
- Publication number
- CN108878960A CN108878960A CN201810719121.XA CN201810719121A CN108878960A CN 108878960 A CN108878960 A CN 108878960A CN 201810719121 A CN201810719121 A CN 201810719121A CN 108878960 A CN108878960 A CN 108878960A
- Authority
- CN
- China
- Prior art keywords
- solid electrolyte
- content
- active material
- lithium
- binder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- 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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
-
- 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
- H01M2300/0082—Organic polymers
-
- 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
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
This disclosure relates to solid electrolyte anode and solid state battery.The solid electrolyte anode includes：Positive plate coated with positive electrode active material layer, and the conductivity ceramics composite coating coated on positive electrode active material layer outer surface, wherein the conductivity ceramics composite coating is with a thickness of 1-50 μm；The conductivity ceramics composite coating includes organic polymer, lithium salts, nano inorganic solid electrolyte, macromolecular grafted modified ceramic, binder and wetting agent, wherein, total weight based on the conductivity ceramics composite coating, the content of the organic polymer is 5~80wt%, the lithium salt content is 5~50wt%, the content of the nano inorganic solid electrolyte is 10~85wt%, the content of the macromolecular grafted modified ceramic is 1~20wt%, the content of the binder is 1~12wt%, and the content of the wetting agent is 0.1~0.5wt%.
Description
Technical field
This disclosure relates to anode field, and in particular to a kind of solid electrolyte anode and the solid-state electricity comprising the anode
Pond.
Background technique
In recent years, in new-energy automobile field, the demand of lithium ion battery increases year by year.Lithium ion battery is generally adopted at present
Ionic conduction is carried out with liquid state organic electrolyte, but organic electrolyte is easy to appear the things such as leakage, corroding electrode, combustion explosion
Therefore there are biggish security risks.
Solid electrolyte battery progresses into the public visual field due to organic liquid battery behavior and higher safety.
Solid electrolyte includes polymer dielectric, inorganic electrolyte and composite electrolyte, under polymer dielectric room temperature conductivity compared with
It is low, inorganic solid electrolyte higher cost, and the poor interfacial resistance between positive/negative plate of current composite electrolyte mechanical performance
It is larger.
Summary of the invention
Present inventor has found through further investigation, coats by using on the conventional cathode surface of solid electrolyte battery
One layer has the conductivity ceramics composite coating of specific composition and prepares solid electrolyte anode, can improve between electrolyte and pole piece
Interface stability and electrochemical operation window, improve lithium ion cycle performance, prepared solid state battery have excellent heat
Stability and mechanical strength properties have high ionic conductivity and lithium ion transference number under room temperature.
On the one hand the disclosure provides a kind of solid electrolyte anode comprising：
Positive plate coated with positive electrode active material layer, and
The conductivity ceramics composite coating coated on positive electrode active material layer outer surface,
The conductivity ceramics composite coating includes organic polymer, lithium salts, nano inorganic solid electrolyte, macromolecular grafted
Modified ceramic, binder and wetting agent, wherein the total weight based on the conductivity ceramics composite coating, the organic polymer
Content be 5~80wt%, the lithium salt content is 5~50wt%, the content of the nano inorganic solid electrolyte is 10~
85wt%, the content of the macromolecular grafted modified ceramic are 1~20wt%, and the content of the binder is 1~12wt%, institute
The content for stating wetting agent is 0.1~0.5wt%.
On the other hand the disclosure is related to the method for preparing above-mentioned solid electrolyte anode, including：
(1) by macromolecular grafted modified ceramic, nano inorganic solid electrolyte and organic polymer, binder, wetting agent
Composite ceramics slurry is mixed to get with solvent；
(2) composite ceramics slurry is coated on outside the positive electrode active material layer of the positive plate coated with positive electrode active material layer
Conductivity ceramics composite coating is dried to obtain behind surface.
Yet another aspect relates to a kind of solid state batteries for the disclosure comprising above-mentioned solid electrolyte anode.
Beneficial effect
In the solid electrolyte anode according to the disclosure, conductivity ceramics composite coating is by organic polymer, lithium salts, nanometer
Inorganic solid electrolyte and the primary coating of submicron order ceramics mixing are formed, and process is simple to operation.Using in organic polymer
Nano inorganic solid electrolyte and submicron order modified ceramic are added in solid electrolyte, provides unobstructed road for lithium ion conduction
Diameter, high rate charge-discharge better performances.In addition, conductivity ceramics composite coating makes lithium ion transfer be evenly distributed, reduce because of lithium branch
Lithium ion caused by crystalline substance is formed loses, and can improve the interface stability and electrochemical operation window between electrolyte and pole piece, mention
High-lithium ion cycle performance.Moreover, introducing macromolecular grafted modified ceramic in conductivity ceramics composite coating, polymer can be upset
Chain reduces polymer crystallinity, improves electrolyte mechanical strength, improves the mechanical performance and chemical property of coating.High score
Sub- graft modification ceramics have the uneven surface structure of micropore interconnection, form multiple fast lithium ion channels, are conducive to lithium ion and expand
It dissipates, while itself ceramic high-temperature stability can also increase the thermal stability of anode.Used nano inorganic solid electrolyte
Large specific surface area and conductivity height, increase lithium ion transferring capability, improve ionic conductivity.The solid electrolyte anode has height
Ionic conductivity, high thermal stability, high-mechanical property and high security.
There is excellent thermal stability and mechanical strength properties according to the solid state battery of the disclosure, there is macroion under room temperature
Conductivity and lithium ion transference number.
Specific embodiment
The disclosure is described in more detail below.
On the one hand the disclosure provides a kind of solid electrolyte anode comprising：
Positive plate coated with positive electrode active material layer, and
The conductivity ceramics composite coating coated on positive electrode active material layer outer surface,
The conductivity ceramics composite coating includes organic polymer, lithium salts, nano inorganic solid electrolyte, macromolecular grafted
Modified ceramic, binder and wetting agent, wherein the total weight based on the conductivity ceramics composite coating, the organic polymer
Content be 5~80wt%, the content of the lithium salts is 5~50%, the content of the nano inorganic solid electrolyte is 10~
85wt%, the content of the macromolecular grafted modified ceramic are 1~20wt%, and the content of the binder is 1~12wt%, institute
The content for stating wetting agent is 0.1~0.5wt%.
The positive electrode active material layer can be coated on the one or both sides of positive plate.Each positive electrode active material layer is thick
Degree can independently be 0.5~50 μm.
It, can be only in a positive electrode active material layer in the case where positive plate two sides are coated with positive electrode active material layer
Applying conductive ceramic composite coating on outer surface, can also on two positive electrode active material layer outer surfaces all applying conductive ceramics
Composite coating.
Conductivity ceramics composite coating thickness independently is 1-100 μm, such as 5~60 μm, preferably 10~50 μm.
In the disclosure, the material of positive plate is not particularly limited, as long as it is to be commonly used for just in this field
The material of pole piece.For example, positive plate can be aluminium foil, thickness can be 8~15 μm.
The positive electrode active material layer includes positive active material, conductive agent and binder, is preferably substantially lived by anode
Property substance, conductive agent and binder composition, wherein the total weight based on positive electrode active material layer, the content of positive active material
It can be 50~95%, preferably 60~85%；The content of conductive agent can be 1~20%, preferably 5~15%；Binder
Content can be 2~30%, preferably 10~25%.
In the disclosure, the positive active material is not particularly limited, if its be commonly used in lithium battery just
Pole active material.For example, the positive active material can for selected from LiMn2O4, cobalt acid lithium, LiFePO4 and ternary just
One of pole material is a variety of.
In the disclosure, the conductive agent is not particularly limited, as long as it is commonly used in the conductive agent of anode.
For example, the conductive agent can be for selected from one of acetylene black, conductive black, carbon fiber, graphene or a variety of.
In the disclosure, the binder is not particularly limited, as long as it is commonly used in the binder of anode.
For example, the binder can be for selected from Kynoar, butadiene-styrene rubber, styrene-acrylic emulsion, acrylic resin, polyacrylonitrile, carboxylic
At least one of sodium carboxymethylcellulose pyce.
The positive electrode active material layer can also include thickener, such as fine selected from carboxymethyl cellulose (CMC), carboxyethyl
Tie up one of element, polyacrylamide, polyurethane or a variety of, wherein the total weight based on positive electrode active material layer, thickener
Content can be 1~10wt%.
According in the solid electrolyte of disclosure anode, conductivity ceramics composite coating may include organic polymer, lithium salts,
Nano inorganic solid electrolyte, macromolecular grafted modified ceramic, binder and wetting agent.In some embodiments, conductive pottery
Porcelain composite coating is substantially by organic polymer, lithium salts, nano inorganic solid electrolyte, macromolecular grafted modified ceramic, bonding
Agent and wetting agent composition." substantially by organic polymer, lithium salts, nano inorganic solid electrolyte, macromolecular grafted modified pottery
Porcelain, binder and wetting agent composition " indicates organic polymer, lithium salts, nano inorganic solid electrolyte, macromolecular grafted modified pottery
Porcelain, binder and wetting agent account for 95wt% or more, the 97wt% or more of conductivity ceramics composite coating, or in some aspects,
99wt% or more.
In conductivity ceramics composite coating, the organic polymer is used to constitute the matrix of organic polyelectrolyte, with
The problems such as evading poor electrolyte leakage, safety that liquid lithium ionic cell is easy to appear, short circuit.The organic polymer can be with
For selected from polyoxyethylene (also referred to as polyethylene oxide (PEO) or polyethylene glycol (PEG)), Kynoar, Kynoar-six
At least one of fluoropropene, poly- ethylene carbonate.
Based on the total weight of the conductivity ceramics composite coating, the content of the organic polymer can be 5~80wt%,
Preferably 15~45wt%, more preferably 20~35wt%.In above-mentioned quantitative range, organic polymer can play raising electricity
Pond safety, flexible effect, gained conductivity ceramics composite coating, finally making solid electrolyte battery, the safety is improved.
In the case where organic polymer content is less than 5wt%, polymer advantage can not be played.It is greater than in organic polymer content
In the case where 80wt%, inorganic solid electrolyte and modified ceramic account for smaller, may cause ionic conducting property decline, high temperature
Shrink aggravation etc..
In conductivity ceramics composite coating, the lithium salts, can be in macromolecule medium by interacting with macromolecule
A degree of negative ions occur to dissociate and be complexed to form complex with high molecular polar group.Polymer segment was wriggled
Cheng Zhong, negative ions are constantly dissociated with original group, and are complexed with neighbouring group, under the action of external electric field, Ke Yishi
The displacement of existing ion, to realize the conduction of negative ions.
Lithium salts is not particularly limited, it can be without restriction using the lithium salts for being suitable for preparing lithium ion battery.For example,
The lithium salts can for selected from lithium hexafluoro phosphate, LiBF4, biethyl diacid lithium borate, LiODFB at least one
Kind.
Based on the total weight of the conductivity ceramics composite coating, the content of the lithium salts can be 5~50wt%, preferably
10~40wt%, more preferably 15~35wt%.In above-mentioned quantitative range, lithium salts can mainly play the work of conducting ion
With.
In one embodiment, in the conductivity ceramics composite coating, the weight ratio of lithium salts and organic polymer is
0.05~10:1, preferably 0.3~3:1.
In conductivity ceramics composite coating, the nano inorganic solid electrolyte has large specific surface area and conductivity is high
Advantage is capable of increasing lithium ion transferring capability, and high temperature resistance and processability are good, high-energy-density large-sized power lithium from
There is good application prospect in sub- battery.
The nano inorganic solid electrolyte can be for selected from lithium lanthanum zirconium oxygen (LLZO), titanium phosphate aluminium lithium (LATP), aluminium lithium
At least one of germanium phosphorus (LAGP).
Based on the total weight of the conductivity ceramics composite coating, the content of the nano inorganic solid electrolyte can be 10
~85wt%, preferably 30~60wt%, more preferably 35~45wt%.In above-mentioned quantitative range, nano inorganic solid electricity
Solution matter can play the role of lithium ion conducting, and gained conductivity ceramics composite coating internal resistance is smaller, and reduce because of interface Li dendrite shape
Lithium ion is lost caused by, improves solid electrolyte battery cycle performance.In nano inorganic solid electrolyte
In the case that content is less than 10wt%, it is lower to may cause conductivity.It is greater than 85wt% in nano inorganic solid electrolyte content
In the case where, it may cause that composite diaphragm mechanical strength is poor, interface impedance when contacting with electrode active material is big and electrification
It is not wide enough to learn window.
The partial size of the nano inorganic solid electrolyte, is indicated with D50, can be 80~500nm, preferably 150~
250nm.In above-mentioned quantitative range, nano inorganic solid electrolyte has the advantages that large specific surface area and conductivity is high, can
Increase lithium ion transferring capability, improve ionic conductivity, so that gained conductivity ceramics composite coating internal resistance is smaller, and reduces because of boundary
Lithium ion is lost caused by face Li dendrite is formed, and improves solid electrolyte battery stability and cycle performance.?
In the case that partial size is less than 80nm, inorganic solid electrolyte particle plug-hole phenomenon may cause, and granularity is smaller, specific surface
Product is larger, easily deposits, and is unfavorable for diaphragm coating.Partial size be greater than 500nm in the case where, may cause material stable structure and
Consistency is low, is unfavorable for lithium ion mobility.
The preparation method of nano inorganic solid electrolyte is not particularly limited, as long as there can be above-mentioned partial size i.e.
It can.Such as submicron order inorganic electrolyte can be crushed to obtain by planetary type ball-milling and/or high-energy ball milling and meet partial size and want
The nano inorganic solid electrolyte asked.
The macromolecular grafted modified ceramic can be the ceramic particle with acrylate copolymer graft modification.Here, third
Olefin(e) acid polymer refers to the homopolymer or copolymer formed by acrylic monomers by homopolymerization or copolymerization.
The glass transition temperature (Tg) of the acrylate copolymer can for 50 DEG C~200 DEG C, preferably 80~180
℃.For example, the acrylate copolymer can be for polymethyl methacrylate or methyl methacrylate and selected from metering system
Acid, ethylacrylic acid, ethyl acrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate one kind or
Several copolymers.
The ceramic particle can be at least one in aluminium oxide, magnesia, magnesium hydroxide, boehmite or calcium carbonate
Kind, partial size is indicated with D50, can be 0.1~8 μm, preferably 0.5~1 μm.
In the macromolecular grafted modified ceramic, the weight ratio of acrylate copolymer and ceramic particle can for 0.01~
0.4：1, preferably 0.05~0.2：1.In weight ratio less than 0.01：In the case where 1, may cause ceramic surface grafting amount compared with
It is low, it is unfavorable for lithium ion transfer, thereby increases and it is possible to cause the mechanical performance of solid electrolyte and chemical property improvement unobvious,
The stabilization at electrochemical stability and interface is not can effectively improve.It is greater than 0.4 in weight ratio：In the case where 1, ceramic watch may cause
Face grafting amount is excessive, and closely interlaced structure may hinder lithium ion tunnel, is unfavorable for lithium ion transfer.
The partial size of the macromolecular grafted modified ceramic, is indicated with D50, can be 0.5 μm~10 μm, preferably 1~6 μ
m。
In the disclosure, D50 refers to partial size corresponding when cumulative distribution is 50% in the size distribution curve of particle,
It can be measured using laser particle analyzer, such as the BetterSize2000 of Dandong Bai Te Instrument Ltd..
It is not limited to any theory, in conductivity ceramics composite coating, the macromolecular grafted modified ceramic has micropore
The uneven surface structure of interconnection is conducive to lithium ion and spreads, while itself ceramic high-temperature stability can also increase the thermostabilization of anode
Property.The macromolecule modified ceramics can upset polymer chain, reduce polymer crystallinity, improve electrolyte mechanical strength.
Based on the total weight of the conductivity ceramics composite coating, the content of the macromolecular grafted modified ceramic can be 1
~20wt%, preferably 5~15wt%, more preferably 5~10wt%.1wt% is less than in macromolecular grafted modified ceramic content
In the case where, it may cause thermal stability decline.It, may in the case where macromolecular grafted modified ceramic content is greater than 20wt%
Lithium ion transferring capability is caused to decline.
The preparation method of macromolecular grafted modified ceramic is not particularly limited, as long as can be by macromolecular grafted to pottery
Porcelain particle surface.
In one embodiment, the preparation of macromolecular grafted modified ceramic is carried out as follows：By acrylic monomers in ceramics
Free yl graft polymerization reaction is carried out in the presence of particle to obtain macromolecular grafted modified ceramic.For example, the free radical grafting
Polymerization reaction can carry out as follows：Under inert gas (such as nitrogen, argon gas) environment, in the presence of ceramic particle, organic
Polymerisation in solution, which is carried out, with radical initiator initiation acrylic monomers in solvent obtains modified ceramic particle.In above-mentioned polymerization reaction
In, the weight ratio of acrylic monomers and ceramic particle can be 0.01~0.4：1, preferably 0.05~0.2：1.For organic molten
The dosage of agent does not specially require, as long as being suitble to carrying out polymerisation in solution.For example, the dosage of the organic solvent can be
Solid content when allowing to carry out polymerisation in solution in mixture is 5~90wt%, preferably 10~80wt%.
In the disclosure, acrylic monomers refers to following formula I compound represented：
Wherein, R1Selected from H and C1-C4 alkyl, R2Selected from H and C1-C10 alkyl.
In embodiments, acrylic monomers includes acrylic acid, acrylate, methacrylic acid, methacrylate, second
Base acrylic acid and ethyl propylene acid esters.In embodiments, described (methyl) acrylic monomers can be poly-methyl methacrylate
Ester or methyl methacrylate with selected from methacrylic acid, ethylacrylic acid, ethyl methacrylate, propyl methacrylate,
One or more of mixtures of butyl methacrylate.
The initiator is not particularly limited, radical initiator commonly used in the art can be used, such as hot
Initiator or ultraviolet initiator, for example, peroxide type initiators, such as persulfate (such as ammonium persulfate etc.), peroxidating
Acyl is (for example, benzoyl peroxide, peroxidating two (2,4- dichloro-benzoyl), diacetyl peroxide, dioctanoyl peroxide and peroxide
Change two lauroyl etc.), alkyl peroxide (for example, dicumyl peroxide, di-tert-butyl peroxide etc.), peroxyester
(such as peroxidized t-butyl perbenzoate, peroxidating pivalic acid tert-butyl ester etc.), hydroperoxide (such as isopropyl benzene hydroperoxide,
Tert-butyl hydroperoxide etc.), peroxy dicarbonate is (for example, dicetyl peroxydicarbonate diisobutyl ester IBP, dicetyl peroxydicarbonate two
Cyclohexyl DCPD, dicetyl peroxydicarbonate two (to t-butyl cyclohexyl methacrylate) etc.) etc., ketone peroxide (such as methyl ethyl ketone peroxide,
Cyclohexanone peroxides etc.), azo initiator is (for example, azodiisobutyronitrile, azobisisoheptonitrile, two NSC 18620 of azo, azo
Diisopropylamidinateand oxazoline etc.), redox initiator etc..Initiator amount can be 0.5~10wt% of ceramic weight, preferably
1~5wt%.
The reaction temperature of free yl graft polymerization reaction is not particularly limited, and can be fitted according to selected initiator
When selection, for example, can be 40~160 DEG C, preferably 60~120 DEG C.Reaction time can be 0.5~24 hour, preferably
It is 1~10 hour.
The organic solvent is not particularly limited, as long as it is poly- to be able to carry out above-mentioned free radical grafting in the organic solvent
Close reaction.For example, the organic solvent can be for selected from tetrahydrofuran, hexamethylene, petroleum ether, acetone, dimethylacetamide
One of amine (DMAC), N,N-dimethylformamide (DMF) are a variety of.
After carrying out free yl graft polymerization reaction, it can also carry out cooling down as needed, filter, drying and other steps.
In conductivity ceramics composite coating, the wetting agent improves its profit with perforated membrane for reducing pulp surface energy
It is moist, avoid the bad phenomenons such as holiday.Wetting agent is not particularly limited, it can be electric using being suitable for preparing lithium without restriction
The wetting agent of pond anode coating.For example, the wetting agent can be for selected from fluoro-alkyl methoxyl group alcohol ether, polyxyethylated
One or more of amine, sodium butylnaphthalenesulfonate, aryl sodium naphthalene sulfonate, neopelex or sodium alkyl sulfate.It is based on
The total weight of the conductivity ceramics composite coating, the content of the wetting agent can be 0.1~0.5wt%, preferably 0.1~
0.4wt%, more preferably 0.15~0.3wt%.In above-mentioned quantitative range, wetting agent, which can play, reduces pulp surface energy
Effect, gained conductivity ceramics composite coating is uniform, and consistency is preferable, finally makes solid electrolyte battery cycle performance good,
Coating and pole piece cementability are preferable.In the case where wetting agent content is less than 0.1wt%, it may cause in slurry coating procedure and fry
It opens, it is bad dotted or large area holiday etc. occurs.In the case where wetting agent content is greater than 0.5wt%, it is saturating to may cause coating
The increase of gas value is more, is unfavorable for lithium ion circulation.
In conductivity ceramics composite coating, the binder avoids battery for bonding coating material and porous basement membrane
Coating shedding when by foreign impacts, influences battery safety.Binder is not particularly limited, can be made without restriction
With the binder for being suitable for preparing lithium battery anode coating.For example, the binder can be for selected from butadiene-styrene rubber (including butylbenzene
Latex), styrene-acrylic emulsion, polyethyl acrylate, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polyvinyl acetate, polyurethane
At least one.Based on the total weight of the conductivity ceramics composite coating, the content of the binder can be 1~12wt%,
Preferably 4~10wt%, more preferably 6~9wt%.In above-mentioned quantitative range, binder can mainly play bonding coat
With the effect of perforated membrane, gained conductivity ceramics composite coating structure is stablized, and proposes solid electrolyte battery security performance
It is high.In the case where binder content is less than 1wt%, it may cause imperfect bonding, i.e., " lose powder ".It is greater than in binder content
In the case where 12wt%, may cause coating breathe freely value it is higher, be unfavorable for lithium ion transfer.
In addition, as needed, conductivity ceramics composite coating can also include dispersing agent (for example, polyacrylamide, polypropylene
Sour sodium, polyoxyethylene dioleate etc.), the addition such as thickener (such as carboxyethyl cellulose, carboxymethyl cellulose (CMC) etc.)
Agent.The dosage of additive can be determined as needed by those skilled in the art, for example, being 0~0.3wt%, based on conduction
The total weight of ceramic composite coating.
According to the solid electrolyte anode of the disclosure can also include other layers, for example, electrostatic spinning layer, hot closed layer,
Nano flame retardant layer.
On the other hand the disclosure is related to the method for preparing above-mentioned solid electrolyte anode, including：
(1) by macromolecular grafted modified ceramic, nano inorganic solid electrolyte and organic polymer, lithium salts, binder, profit
Humectant and solvent are mixed to get composite ceramics slurry；
(2) composite ceramics slurry is coated on outside the positive electrode active material layer of the positive plate coated with positive electrode active material layer
Conductivity ceramics composite coating is dried to obtain behind surface.
In above-mentioned steps (1), for macromolecular grafted modified ceramic, nano inorganic solid electrolyte, organic polymer,
The description of lithium salts, binder and wetting agent is identical as foregoing teachings, is not repeated herein.
The solvent is not particularly limited, as long as the solvent can make macromolecular grafted modified ceramic, lithium salts, You Jiju
Object, binder and wetting agent is closed to be uniformly dispersed.For example, the solvent can be for selected from deionized water or distilled water, tetrahydro
One of furans, hexamethylene, petroleum ether, acetone, dimethyl acetamide (DMAC), N,N-dimethylformamide (DMF) are more
Kind.
The dosage of the solvent is not particularly limited, as long as gained composite ceramics slurry is enabled to be suitable for being coated in just
On pole piece.In one embodiment, the dosage of the solvent makes the solid content of the slurry be 10-60wt%, example
Such as 15~50wt%, preferably 20~45wt%.
In above-mentioned steps (1), the method that each component is mixed with composite ceramics slurry is not particularly limited, only
It wants each component can uniformly be mixed.For example, can be stirred using planetary stirring machine, homogenizer etc..
Method in above-mentioned steps (2), for being coated on composite ceramics slurry on positive electrode active material layer outer surface
It is not particularly limited, as long as uniform coating can be obtained.For example, can be applied using micro- plate gravure coating method
It covers.After coating, the method for dry coating is not particularly limited, as long as can be by solvent removing and not unfavorable to coating generation
Influence.For example, can be using the methods of drying, vacuum drying.
In one embodiment, step (2) carries out as follows, and composite ceramics slurry coating method is coated on and is coated with just
The one or both sides of the positive plate of pole active material layer, coating speed are 20~80m/min, are dried using 30~60 DEG C of ovens
It is dry, obtain conductivity ceramics composite coating.
The thickness of composite ceramic conductive coating is each independently 1~100 μm, such as 5~60 μm, preferably 10~50 μ
m。
In above-mentioned steps (2), the description about the positive plate for being coated with positive electrode active material layer is identical as foregoing teachings,
It is not repeated herein.The method for preparing the positive plate coated with positive electrode active material layer is not particularly limited, it can be with
It is prepared using method as known in the art.
In one embodiment, the positive plate coated with positive electrode active material layer can be prepared as follows：
1) positive active material, N-Methyl pyrrolidone (NMP), binder, conductive agent are uniformly mixed, obtain positive work
Property compound paste,
2) one or both sides that above-mentioned anode active material slurry is coated on positive plate are formed into positive electrode active material layer simultaneously
It is dry, thus obtain the positive plate coated with positive electrode active material layer.
In one embodiment, in above-mentioned steps 1) in, for example, positive active material, NMP can be mixed,
25~40 DEG C of temperature, 500~2500rpm/min of revolving speed, 1~3h of time；Then binder, conductive agent are added, temperature 25 is kept
~40 DEG C, after stirring 0.5~2h under 1000~2000rpm/min, obtain anode active material slurry.
In above-mentioned steps 2) in, the method that anode active material slurry is coated on positive plate is not limited especially
System, as long as uniform coating can be obtained.For example, can be coated using micro- plate gravure coating method.After coating,
The method of dry coating is not particularly limited, as long as can remove and not have an adverse effect to coating by solvent.
For example, can be using the methods of drying, vacuum drying.
According to the method for preparing solid electrolyte anode of the disclosure can also as needed include prepare electrostatic spinning layer,
The operation such as hot closed layer, nano flame retardant layer.It is above-mentioned to prepare the operations such as electrostatic spinning layer, hot closed layer, nano flame retardant layer and adopt
It is carried out with the routine operation for preparing these layers in this field.
According to the method for preparing solid electrolyte anode of the disclosure can also carry out as needed pole piece pressure roller, slitting,
The operation such as film-making.The operations such as the pole piece pressure roller, slitting, film-making can using prepare in this field the routine operation of anode into
Row, such as can be by compacted density 3.85g/cm3Carry out pole piece pressure roller.
The another aspect of the disclosure provides a kind of solid state battery comprising above-mentioned solid electrolyte anode.
Other than above-mentioned solid electrolyte anode, the solid state battery can have the routine of solid state battery in this field
Structure and component, for example, further including cathode and aluminum plastic film etc..
Cathode and aluminum plastic film are not particularly limited, any can be used for solid state battery using as known in the art
Cathode and aluminum plastic film.
In one embodiment, the cathode may include negative electrode tab and coated on the negative electrode active material in negative electrode tab
Layer.
In one embodiment, the negative electrode tab be copper foil, 5~20 μm of thickness.
The negative electrode active material is not particularly limited, as long as it is the active matter for cathode commonly used in the art
Matter.For example, negative electrode active material can for selected from artificial graphite, natural graphite it is one or more.
In one embodiment, the solid state battery is solid state lithium battery.
In addition, the structure and assemble method for solid state battery also without any specifically limited, can use in this field
Known any structure that can be used for lithium battery and assemble method.Such as the solid state battery can be assembled into button cell, side
Shape battery etc..
The disclosure is hereinbefore described in detail, but above embodiment is substantially only illustrative, and simultaneously
It is not intended to limit the disclosure.In addition, not appointed herein by described in the aforementioned prior art or summary of the invention or following embodiment
What theoretical limitation.
Unless expressly stated otherwise, the numberical range in entire application documents includes any subrange therein and with it
The incremental any numerical value of the minimum subunit of middle given value.Unless expressly stated otherwise, the numerical tabular in entire application documents
Show to including implementation with the little deviation of given value and with about mentioned value and with mentioned exact value
The approximate measure or limitation of the range of scheme.Other than the working Examples finally provided in detailed description, present specification
All numerical value of parameter (for example, quantity or condition) in (including appended claims) shall be construed as in all cases
It is modified by term " about ", before whether actually appearing in the numerical value regardless of " about "." about " indicate that the numerical value allows
It is slightly inaccurate (to have at this value some close to accurate；Approximately or reasonably close to the value；It is approximate).If " about " provided
Inexactness does not understand that " about " then used herein at least indicates to pass through in the art with this ordinary meaning
The variation of measurement and the commonsense method generation using these parameters.For example, " about " may include being less than or equal to 10%, it is less than
Or it is equal to 5%, it is less than or equal to 4%, is less than or equal to 3%, is less than or equal to 2%, less than or equal to 1% or is less than or waits
Variation in 0.5% variation, and in some aspects, less than or equal to 0.1%.
Unless expressly stated otherwise, the term "comprising" in entire application documents, " comprising ", " having ", " containing " or
Other any similar terms belong to open term, indicate a composition or product in addition to including listed herein these
Other than element, it may also include not expressly listed but composition or the usual intrinsic other element of product.In addition, herein
In, the interpretation of term "comprising", " comprising ", " having ", " containing " should be regarded as specifically disclosing and cover simultaneously " by ... institute's group
At " and the closed or semi-enclosed conjunction such as " substantially by ... formed "." substantially by ... formed " indicates this paper institute
These elements listed account for 95% or more of the composition or product, 97% or more, or in some aspects, and 99% or more.
Embodiment
The technical solution of the disclosure is further illustrated below by embodiment.Those skilled in the art are it will be clearly understood that institute
It states embodiment and is only to aid in and understand the disclosure, be not construed as the concrete restriction to the disclosure.
Reagent and instrument
Unless otherwise indicated, agents useful for same is the commercially available reagent suitable for lithium battery.Unless otherwise indicated, identical
Term refers to identical material.Kynoar is purchased from Dongguan City Li Heng plastic material Co., Ltd.LiFePO4, LiMn2O4 purchase
From Guizhou Anda Technology Energy Co., Ltd..Tertiary cathode material is purchased from Hunan Shanshan New Materials Co., Ltd.Partial size D50
It is detected with laser particle analyzer (Dandong Bai Te Instrument Ltd., BetterSize2000).
Prepare embodiment
The preparation of cathode
1) 32g natural graphite, 6g Kynoar, 60g deionized water are mixed into planetary stirring of going forward side by side, temperature 35
DEG C, revolving speed 1500rpm/min, time 2h；Then 2g acetylene black is added, is kept for 35 DEG C of temperature, after 1000rpm/min stirs 1h,
Obtain watersoluble plumbago slurry；
2) after above-mentioned watersoluble plumbago slurry being crossed 300 mesh screens, copper foil one or both sides is coated on and form equadag coating, are dried
It is dry, apply 20 μm of thickness.Then roll-in, slitting, film-making are carried out, cathode is obtained.
Embodiment 1
The preparation of the positive plate of phosphoric acid iron lithium
1) 50g LiFePO4,130g N-Methyl pyrrolidone (NMP) are mixed, 30 DEG C of temperature, revolving speed
1500rpm/min, time 3h；Then styrene-acrylic emulsion, 6g carbon fiber that addition 20g solid content is 50wt%, are kept for 30 DEG C of temperature,
After stirring 1.5h under 1000rpm/min, anode composite slurry is obtained；
2) above-mentioned anode composite slurry is coated on to the one or both sides of 10 μm of aluminium foils of thickness, is then dried, single coating is thick
42 μm of degree, obtains the positive plate of phosphoric acid iron lithium.
Macromolecular grafted modified ceramic preparation：
In a nitrogen environment, 1.5g benzoyl peroxide is added in 100ml tetrahydrofuran, is stirred to being completely dissolved, so
7.5g methyl methacrylate and 75g alumina particulate (D50=1.0 μm), 80 DEG C of back flow reaction 5h are added afterwards, cooling filters,
Modified ceramic particle (D50=1.5 μm) is obtained after vacuum drying 10h.
The preparation of nano inorganic solid electrolyte：
Submicron order LLZO crushes to obtain a nanometer LLZO by planetary type ball-milling and high-energy ball milling, and partial size D50 is 210nm.
The preparation of solid electrolyte anode：
Using 20g as the polyoxyethylene of organic polymer and 6.85g as the polyvinyl acetate of binder 150ml's
It is uniformly dispersed in DMAC, then proceedes to the macromolecular grafted modified ceramic particle that lithium hexafluoro phosphate (30g), aforementioned preparation is added
(6g) and nanometer LLZO (35g) is eventually adding 0.15g and mixes in 1L reaction kettle as the polyoxyethylene alkyl amine of wetting agent and stirs
It mixes 3h and obtains composite ceramics slurry.
Composite ceramics slurry is coated on to the one or both sides of the positive plate of phosphoric acid iron lithium prepared above, using
120 DEG C of vacuum drying 48h, obtain conductivity ceramics composite coating, and 40 μm of final coating thickness；Then compacted density 3.85g/ is pressed
cm3Roll-in, slitting, film-making are carried out, solid electrolyte anode is obtained.
The preparation of solid state battery：
The cathode of above-mentioned solid electrolyte anode and aforementioned preparation is successively wound 10 layers into the rectangular solid state battery of lithium ion.
Embodiment 2
The preparation of positive plate containing LiMn2O4
1) 50g LiMn2O4,130g N-Methyl pyrrolidone (NMP) are mixed, 30 DEG C of temperature, revolving speed 1500rpm/
Min, time 3h；Then styrene-acrylic emulsion, 6g carbon fiber that addition 20g solid content is 50wt%, are kept for 30 DEG C of temperature, 1000rpm/
After stirring 1.5h under min, anode composite slurry is obtained；
2) above-mentioned anode composite slurry is coated on to the one or both sides of 10 μm of aluminium foils of thickness, is then dried, single coating is thick
42 μm of degree, obtains the positive plate containing LiMn2O4.
Macromolecular grafted modified ceramic preparation：
In a nitrogen environment, by 1.5g benzoyl peroxide be added 100ml acetone in, stir to being completely dissolved, then plus
Enter 7.5g methyl methacrylate and ethylacrylic acid (ratio 1:1) with 75g magnesium oxide particle (D50=0.9 μm), 80 DEG C are flowed back
6h is reacted, cooling, suction filtration obtains modified ceramic particle (D50=1.3 μm) after being dried in vacuo 8h.
The preparation of nano inorganic solid electrolyte：
Submicron order LLZO crushes to obtain a nanometer LLZO by planetary type ball-milling and high-energy ball milling, and partial size D50 is 240nm.
The preparation of solid electrolyte anode：
Using 20g as the Kynoar of organic polymer and 6.85g as the polyvinyl acetate of binder in 150ml
N,N-Dimethylformamide in be uniformly dispersed, then proceed to be added lithium hexafluoro phosphate (30g), aforementioned preparation it is macromolecular grafted
Modified ceramic particle (6g), nanometer LLZO (35g), the polyoxyethylene alkyl amine that 0.2g is then added as wetting agent are reacted in 1L
3h is mixed in kettle and obtains composite ceramics slurry.
Composite ceramics slurry is coated on to the one or both sides of the positive plate containing LiMn2O4, is dried in vacuo using 120 DEG C
48h obtains conductivity ceramics composite coating, 35 μm of final single coating thickness；Then compacted density 3.85g/cm is pressed3Progress roll-in,
Slitting, film-making obtain solid electrolyte anode.
The preparation of solid state battery：
Above-mentioned solid electrolyte anode and the cathode of aforementioned preparation successively wind 10 layers and the rectangular solid state battery of lithium ion are made.
Embodiment 3
The preparation of positive plate containing tertiary cathode material
1) 50g tertiary cathode material, 130g N-Methyl pyrrolidone (NMP) are mixed, 30 DEG C of temperature, revolving speed
1500rpm/min, time 3h；Then styrene-acrylic emulsion, 6g carbon fiber that addition 20g solid content is 50wt%, are kept for 30 DEG C of temperature,
After stirring 1.5h under 1000rpm/min, anode composite slurry is obtained；
2) above-mentioned anode composite slurry is coated on to the one or both sides of 10 μm of aluminium foils of thickness, is then dried, single coating is thick
42 μm of degree, obtains the positive plate containing tertiary cathode material.
The preparation of macromolecular grafted modified ceramic：
In a nitrogen environment, 1.5g benzoyl peroxide is added in 100ml tetrahydrofuran, is stirred to being completely dissolved, so
15g ethyl methacrylate and methacrylic acid (ratio 1 are added afterwards:1) and 75g boehmite particulate (D50=0.9 μm), 80 DEG C
Back flow reaction 10h, cooling, suction filtration, obtains modified ceramic particle (D50=1.4 μm) after being dried in vacuo 6h.
The preparation of nano inorganic solid electrolyte：
Submicron order LATP crushes to obtain a nanometer LATP by planetary type ball-milling and high-energy ball milling, and partial size D50 is 200nm.
The preparation of solid electrolyte anode：
20g is existed as the poly- ethylene carbonate of organic polymer and 6.85g as the polyvinyl acetate of binder
It is uniformly dispersed in the n,N-Dimethylformamide of 150ml, then proceedes to the high score that lithium hexafluoro phosphate (30g), aforementioned preparation is added
Sub- graft modification ceramic particle (6g), nanometer LLZO (35g) are then added 0.2g and exist as the polyoxyethylene alkyl amine of wetting agent
3h is mixed in 1L reaction kettle and obtains composite ceramics slurry.
Composite ceramics slurry is coated on to the one or both sides of the positive plate containing tertiary cathode material, by 150 DEG C of vacuum
Drying for 24 hours, obtains conductivity ceramics composite coating, 35 μm of final single coating thickness；Then compacted density 3.85g/cm is pressed3Carry out roller
Pressure, slitting, film-making obtain solid electrolyte anode.
The preparation of solid state battery：
The cathode of above-mentioned solid electrolyte anode and aforementioned preparation is successively wound 10 layers into the rectangular solid state battery of lithium ion.
Comparative example 1
The preparation of nano inorganic solid electrolyte：
Submicron order LLZO crushes to obtain a nanometer LLZO by planetary type ball-milling and high-energy ball milling, and partial size D50 is 210nm.
The preparation of solid electrolyte anode：
The above-mentioned nanometer LLZO of 32g is dissolved into 70ml DMAC, polyvinyl acetate of the 3.8g as binder is then added
Ester, 0.2g are mixed 3h as the polyoxyethylene alkyl amine of wetting agent in 1L reaction kettle and obtain inorganic electrolyte slurry.
35g is added in the DMAC of 105ml as the polyoxyethylene of organic polymer and 30g lithium hexafluoro phosphate and is dispersed with stirring
Uniformly, it is anti-in 1L as the polyoxyethylene alkyl amine of wetting agent as polyvinyl acetate, the 0.2g of binder that 10g is then added
Mixing 3h in kettle is answered to obtain organic polyelectrolyte slurry.
Above-mentioned organic polyelectrolyte slurry is coated on to the side or two of the positive plate of the phosphoric acid iron lithium of embodiment 1
Side for 24 hours by 150 DEG C of vacuum drying obtains organic polyelectrolyte coating, 20 μm of final single coating thickness.
Above-mentioned inorganic electrolyte slurry is coated on organic polyelectrolyte coating outer surface, it is dry by 120 DEG C of vacuum
Dry 36h obtains inorganic electrolyte coating, 15 μm of final single coating thickness；Then it carries out by compacted density 3.85g/cm3Roll-in,
Slitting, film-making obtain solid electrolyte anode.
The preparation of solid state battery
The cathode of above-mentioned solid electrolyte anode and aforementioned preparation is successively wound 10 layers into the rectangular solid state battery of lithium ion.
Comparative example 2
The preparation of aluminium oxide ceramics diaphragm
The aluminium oxide that 30g partial size is 1 μm is added in 200g deionized water, is stirred evenly, 20g solid content, which is then added, is
The polyoxyethylene alkyl amine as the butadiene-styrene latex and 1g of binder as wetting agent of 50wt%, stirring 2.5h are uniformly dispersed,
Obtain ceramic slurry.
Above-mentioned ceramic slurry is coated on the PE basement membrane of 12 μ m-thicks, 50 DEG C of oven dryings obtain aluminium oxide ceramics diaphragm,
4 μm of single ceramic coating layer thickness, coating weight 5g/m2。
The preparation of battery
Successively by the positive plate of the phosphoric acid iron lithium of embodiment 1, above-mentioned aluminium oxide ceramics diaphragm and the cathode of aforementioned preparation
Wind 10 layers of squarely aluminum-shell battery.
Then electrolyte is injected by battery after being dried in vacuo and vacuumizing moisture removal, in shell (containing 1mol/L's
LiPF6Organic electrolyte, wherein solvent be dimethyl carbonate：Diethyl carbonate：Propene carbonate=1:1:1) it, seals.?
To organic solution lithium ion battery.
Experimental example
The battery pack (including 5 batteries) for extracting embodiment 1-3 and comparative example 1-2 carries out cycle performance test after completely filling.
Lithium ion battery is used at normal temperature 1C multiplying power charge, 1C multiplying power discharging, successively carry out 500 times circulation, record circulation before and
Battery capacity after circulation every time (every group takes 5 battery data average values).
Capacity retention ratio=(battery capacity before battery capacity/circulation after n times circulation) × 100% after n times circulation.
Capacity retention ratio the results are shown in Table 1 after 500 circulations：
Capacity retention ratio (%) after table 1 500 times circulations
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 |
| Capacity retention ratio % | 97.42% | 96.85% | 96.31% | 91.43% | 89.48% |
As can be seen from Table 1, the capacity retention ratio of Examples 1 to 3 battery is higher, it may be possible to reduce in cyclic process
Lithium ion irreversible loss amount has high ionic conductivity, reduces the influence of shuttle effect, avoids Li dendrite and formed.
The capacity retention ratio of 1 battery of comparative example takes second place, and organic bath blanket clip is living in high conductivity inorganic electrolyte coating and anode
Between property material layer, cycle performance of battery is improved to a certain extent.The capacity retention ratio of 2 battery of comparative example is lower, is recycling
Internal resistance is larger in the process, is unfavorable for cycle performance of lithium ion battery.
Claims (10)
1. a kind of solid electrolyte anode comprising：
Positive plate coated with positive electrode active material layer, and
The conductivity ceramics composite coating coated on positive electrode active material layer outer surface,
The conductivity ceramics composite coating includes organic polymer, lithium salts, nano inorganic solid electrolyte, macromolecular grafted modification
Ceramics, binder and wetting agent, wherein the total weight based on the conductivity ceramics composite coating, the organic polymer contain
Amount is 5~80wt%, and the content of the lithium salts is 5~50%, the content of the nano inorganic solid electrolyte is 10~
85wt%, the content of the macromolecular grafted modified ceramic are 1~20wt%, and the content of the binder is 1~12wt%, institute
The content for stating wetting agent is 0.1~0.5wt%.
2. solid electrolyte according to claim 1 anode, wherein the conductivity ceramics composite coating with a thickness of 1-
100 μm, such as 5~60 μm, preferably 10~50 μm.
3. solid electrolyte anode according to claim 1, wherein
The organic polymer is selected from polyoxyethylene, Kynoar, Kynoar-hexafluoropropene, poly- ethylene carbonate
At least one；And/or
The lithium salts be selected from lithium hexafluoro phosphate, LiBF4, biethyl diacid lithium borate, LiODFB at least one
Kind；And/or
The nano inorganic solid electrolyte is at least one selected from lithium lanthanum zirconium oxygen, titanium phosphate aluminium lithium, aluminium lithium germanium phosphorus；It is preferred that its
Partial size indicates with D50, is 80~500nm, preferably 150~250nm, and/or
The wetting agent is selected from fluoro-alkyl methoxyl group alcohol ether, polyoxyethylene alkyl amine, sodium butylnaphthalenesulfonate, aryl naphthalene sulfonic acids
One or more of sodium, neopelex or sodium alkyl sulfate；And/or
The binder is selected from butadiene-styrene rubber, styrene-acrylic emulsion, polyethyl acrylate, polyvinyl alcohol, ethene-vinyl acetate copolymerization
At least one of object, polyvinyl acetate, polyurethane.
4. solid electrolyte anode according to claim 1, wherein the gross weight based on the conductivity ceramics composite coating
Amount,
The content of the organic polymer is 15~45wt%, preferably 20~35wt%；And/or
The content of the lithium salts is 10~40wt%, preferably 15~35wt%；And/or
The content of the nano inorganic solid electrolyte is 30~60wt%, preferably 35~45wt%；And/or
The content of the macromolecular grafted modified ceramic is 5~15wt%, preferably 5~10wt%；And/or
The content of the wetting agent is 0.1~0.4wt%, preferably 0.15~0.3wt%；And/or
The content of the binder is 4~10wt%, preferably 6~9wt%；And/or
Preferably, in the conductivity ceramics composite coating, the weight ratio of lithium salts and organic polymer is 0.05~10:1, preferably
It is 0.3~3:1.
5. solid electrolyte anode according to claim 1, wherein the macromolecular grafted modified ceramic is to use acrylic acid
The ceramic particle of polymer graft modification；
Preferably, the glass transition temperature of the acrylate copolymer is 50 DEG C~200 DEG C, preferably 80~180 DEG C；
Preferably, the acrylate copolymer for polymethyl methacrylate or methyl methacrylate and is selected from metering system
Acid, ethylacrylic acid, ethyl acrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate one kind or
Several copolymers；
Preferably, the ceramic particle is at least one in aluminium oxide, magnesia, magnesium hydroxide, boehmite or calcium carbonate
Kind, partial size is indicated with D50, is 0.1~8 μm, preferably 0.5~1 μm；
Preferably, in the macromolecular grafted modified ceramic, the weight ratio of acrylate copolymer and ceramic particle is 0.01~
0.4：1, preferably 0.05~0.2：1；
Preferably, the partial size of the macromolecular grafted modified ceramic, is indicated with D50, is 0.5 μm~10 μm, preferably 1~6 μm.
6. solid electrolyte anode according to claim 5, wherein the macromolecular grafted modified ceramic is prepared as follows：
Acrylic monomers is carried out to free yl graft polymerization reaction in the presence of ceramic particle to obtain macromolecular grafted modified ceramic；
Preferably, in above-mentioned polymerization reaction, the weight ratio of acrylic monomers and ceramic particle is 0.01~0.4：1, preferably
0.05~0.2：1；
Preferably, the acrylic monomers for methyl methacrylate or methyl methacrylate and is selected from methacrylic acid, second
The mixtures of base acrylic acid, ethyl methacrylate, the one or more of propyl methacrylate, butyl methacrylate；
Preferably, initiator amount is 0.5~10%, preferably the 1~5% of ceramic weight.
7. solid electrolyte anode according to claim 1, wherein
The positive electrode active material layer is coated on the one or both sides of positive plate, and each positive electrode active material layer thickness is independently
It is 0.5~50 μm；And/or
Positive plate is aluminium foil, with a thickness of 8~15 μm；And/or
The positive electrode active material layer includes positive active material, conductive agent and binder, wherein is based on positive electrode active material layer
Total weight, the content of positive active material is 50~95%, preferably 60~85%；The content of conductive agent is 1~20%, excellent
It is selected as 5~15%；The content of binder is 2~30%, preferably 10~25%；And/or
The positive active material is selected from one of LiMn2O4, cobalt acid lithium, LiFePO4 and tertiary cathode material or a variety of；
And/or
The conductive agent is selected from one of acetylene black, conductive black, carbon fiber, graphene or a variety of；And/or
The binder is fine selected from Kynoar, butadiene-styrene rubber, styrene-acrylic emulsion, acrylic resin, polyacrylonitrile, carboxymethyl
Tie up at least one of plain sodium.
8. a kind of method for preparing solid electrolyte anode of any of claims 1-7, including：
(1) by macromolecular grafted modified ceramic, nano inorganic solid electrolyte and organic polymer, lithium salts, binder, wetting agent
Composite ceramics slurry is mixed to get with solvent；
(2) composite ceramics slurry is coated on to the positive electrode active material layer outer surface of the positive plate coated with positive electrode active material layer
After be dried to obtain conductivity ceramics composite coating.
9. according to the method described in claim 8, wherein,
The solvent be selected from deionized water or distilled water, tetrahydrofuran, hexamethylene, petroleum ether, acetone, dimethyl acetamide,
One of N,N-dimethylformamide is a variety of；
Preferably, the dosage of the solvent makes the solid content of the slurry for 10-60wt%, such as 15~50wt%, preferably
For 20~45wt%.
10. a kind of solid state battery, such as solid state lithium battery comprising solid electrolyte of any of claims 1-7
Anode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810719121.XA CN108878960B (en) | 2018-07-03 | 2018-07-03 | Solid electrolyte positive electrode and solid battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810719121.XA CN108878960B (en) | 2018-07-03 | 2018-07-03 | Solid electrolyte positive electrode and solid battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108878960A true CN108878960A (en) | 2018-11-23 |
| CN108878960B CN108878960B (en) | 2020-06-09 |
Family
ID=64298426
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810719121.XA Expired - Fee Related CN108878960B (en) | 2018-07-03 | 2018-07-03 | Solid electrolyte positive electrode and solid battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108878960B (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110957464A (en) * | 2019-09-25 | 2020-04-03 | 东莞赣锋电子有限公司 | Preparation of coated pole piece |
| CN111509186A (en) * | 2020-05-22 | 2020-08-07 | 清陶（昆山）能源发展有限公司 | Lithium ion solid-state battery anode, preparation process thereof and lithium ion solid-state battery |
| CN111697204A (en) * | 2019-03-12 | 2020-09-22 | 杭州众达新能源材料有限公司 | Lithium lanthanum zirconium oxide/lithium cobaltate composite material and preparation method and application thereof |
| CN112542558A (en) * | 2019-09-20 | 2021-03-23 | 青岛九环新越新能源科技股份有限公司 | Double-roller coating method for solid energy storage electrode strip |
| CN112687971A (en) * | 2020-12-28 | 2021-04-20 | 中国电子科技集团公司第十八研究所 | Self-repairing functional interface layer of solid-state battery and construction method |
| CN112909430A (en) * | 2019-12-03 | 2021-06-04 | 恒大新能源技术(深圳)有限公司 | Lithium ion battery diaphragm and preparation method thereof and lithium ion battery |
| CN113036131A (en) * | 2019-12-09 | 2021-06-25 | 财团法人工业技术研究院 | Positive electrode material, positive electrode containing same, and battery |
| CN113113569A (en) * | 2021-04-09 | 2021-07-13 | 常州赛得能源科技有限公司 | High-rate long-cycle lithium ion battery |
| CN113270637A (en) * | 2020-02-14 | 2021-08-17 | 通用汽车环球科技运作有限责任公司 | Lithium phosphate coating for lithium lanthanum zirconium oxide solid electrolyte powder |
| CN113764615A (en) * | 2021-09-09 | 2021-12-07 | 珠海冠宇电池股份有限公司 | Positive electrode and electrochemical device containing same |
| CN113937250A (en) * | 2020-06-29 | 2022-01-14 | 珠海冠宇电池股份有限公司 | Positive pole piece and solid-state battery containing same |
| CN114335710A (en) * | 2021-12-17 | 2022-04-12 | 西安交通大学 | Preparation method and application of double-modified solid electrolyte membrane |
| CN114583246A (en) * | 2022-02-21 | 2022-06-03 | 南昌大学 | Solid-state lithium ion battery and preparation method thereof |
| CN116111038A (en) * | 2023-04-12 | 2023-05-12 | 四川新能源汽车创新中心有限公司 | Electrode plate, preparation method thereof and lithium battery |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104064709A (en) * | 2014-06-09 | 2014-09-24 | 东莞市魔方新能源科技有限公司 | Ceramic membrane, preparation method of lithium ion secondary battery and battery |
| CN105098234A (en) * | 2015-09-22 | 2015-11-25 | 中国科学院物理研究所 | Solid electrolyte material, and electrolyte layer and lithium ion battery comprising solid electrolyte material |
| CN105914396A (en) * | 2016-06-01 | 2016-08-31 | 浙江大学 | Preparation method of ultrathin nano-lithium lanthanum zirconium oxygen all-solid-state electrolyte layer |
| CN106785009A (en) * | 2016-12-09 | 2017-05-31 | 北京科技大学 | A kind of all solid state composite electrolyte of organic-inorganic and its methods for making and using same |
| CN107134587A (en) * | 2017-04-26 | 2017-09-05 | 华中科技大学 | A kind of solid electrolyte inorganic nano particle filler and preparation method thereof |
| CN107645013A (en) * | 2016-07-22 | 2018-01-30 | 中国科学院物理研究所 | Compound quasi-solid electrolyte, its preparation method and the lithium battery or lithium ion battery containing it |
-
2018
- 2018-07-03 CN CN201810719121.XA patent/CN108878960B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104064709A (en) * | 2014-06-09 | 2014-09-24 | 东莞市魔方新能源科技有限公司 | Ceramic membrane, preparation method of lithium ion secondary battery and battery |
| CN105098234A (en) * | 2015-09-22 | 2015-11-25 | 中国科学院物理研究所 | Solid electrolyte material, and electrolyte layer and lithium ion battery comprising solid electrolyte material |
| CN105914396A (en) * | 2016-06-01 | 2016-08-31 | 浙江大学 | Preparation method of ultrathin nano-lithium lanthanum zirconium oxygen all-solid-state electrolyte layer |
| CN107645013A (en) * | 2016-07-22 | 2018-01-30 | 中国科学院物理研究所 | Compound quasi-solid electrolyte, its preparation method and the lithium battery or lithium ion battery containing it |
| CN106785009A (en) * | 2016-12-09 | 2017-05-31 | 北京科技大学 | A kind of all solid state composite electrolyte of organic-inorganic and its methods for making and using same |
| CN107134587A (en) * | 2017-04-26 | 2017-09-05 | 华中科技大学 | A kind of solid electrolyte inorganic nano particle filler and preparation method thereof |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111697204A (en) * | 2019-03-12 | 2020-09-22 | 杭州众达新能源材料有限公司 | Lithium lanthanum zirconium oxide/lithium cobaltate composite material and preparation method and application thereof |
| CN112542558A (en) * | 2019-09-20 | 2021-03-23 | 青岛九环新越新能源科技股份有限公司 | Double-roller coating method for solid energy storage electrode strip |
| CN110957464A (en) * | 2019-09-25 | 2020-04-03 | 东莞赣锋电子有限公司 | Preparation of coated pole piece |
| CN110957464B (en) * | 2019-09-25 | 2021-08-17 | 东莞赣锋电子有限公司 | Preparation method of coated pole piece |
| CN112909430A (en) * | 2019-12-03 | 2021-06-04 | 恒大新能源技术(深圳)有限公司 | Lithium ion battery diaphragm and preparation method thereof and lithium ion battery |
| CN113036131A (en) * | 2019-12-09 | 2021-06-25 | 财团法人工业技术研究院 | Positive electrode material, positive electrode containing same, and battery |
| CN113270637A (en) * | 2020-02-14 | 2021-08-17 | 通用汽车环球科技运作有限责任公司 | Lithium phosphate coating for lithium lanthanum zirconium oxide solid electrolyte powder |
| CN111509186A (en) * | 2020-05-22 | 2020-08-07 | 清陶（昆山）能源发展有限公司 | Lithium ion solid-state battery anode, preparation process thereof and lithium ion solid-state battery |
| CN113937250A (en) * | 2020-06-29 | 2022-01-14 | 珠海冠宇电池股份有限公司 | Positive pole piece and solid-state battery containing same |
| CN113937250B (en) * | 2020-06-29 | 2022-08-30 | 珠海冠宇电池股份有限公司 | Positive pole piece and solid-state battery containing same |
| CN112687971A (en) * | 2020-12-28 | 2021-04-20 | 中国电子科技集团公司第十八研究所 | Self-repairing functional interface layer of solid-state battery and construction method |
| CN113113569A (en) * | 2021-04-09 | 2021-07-13 | 常州赛得能源科技有限公司 | High-rate long-cycle lithium ion battery |
| CN113764615A (en) * | 2021-09-09 | 2021-12-07 | 珠海冠宇电池股份有限公司 | Positive electrode and electrochemical device containing same |
| CN114335710A (en) * | 2021-12-17 | 2022-04-12 | 西安交通大学 | Preparation method and application of double-modified solid electrolyte membrane |
| CN114583246A (en) * | 2022-02-21 | 2022-06-03 | 南昌大学 | Solid-state lithium ion battery and preparation method thereof |
| CN116111038A (en) * | 2023-04-12 | 2023-05-12 | 四川新能源汽车创新中心有限公司 | Electrode plate, preparation method thereof and lithium battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108878960B (en) | 2020-06-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108878960A (en) | Solid electrolyte anode and solid state battery | |
| CN108878751B (en) | Conductive ceramic composite diaphragm and solid-state battery | |
| CN109004265B (en) | Solid electrolyte positive electrode and solid battery comprising same | |
| CN107665966A (en) | A kind of lithium-sulfur cell | |
| KR102408332B1 (en) | Conductive resin composition and electrode composition for electrode, electrode and lithium ion battery using same | |
| CN111725509B (en) | Negative electrode material, negative electrode slurry, negative electrode plate and lithium ion battery | |
| CN108987800A (en) | Solid electrolyte and preparation method thereof and solid state battery containing the solid electrolyte | |
| CN107437603A (en) | Composite diaphragm for lithium ion battery and preparation method thereof and lithium ion battery | |
| CN109509857A (en) | A kind of porosity lithium ion battery separator and its application with inierpeneirating network structure | |
| CN101747642B (en) | Gel polymer electrolyte, polymer battery and preparing method | |
| CN111533851A (en) | Preparation method of polymer electrolyte and application of polymer electrolyte in all-solid-state battery | |
| CN107710470B (en) | Binder for negative electrode of lithium ion secondary battery, slurry composition for negative electrode, and lithium ion secondary battery | |
| CN109841785A (en) | A kind of battery diaphragm and preparation method thereof and the lithium ion battery comprising the diaphragm | |
| CN107785521A (en) | A kind of battery diaphragm and lithium ion battery and preparation method thereof | |
| CN106328935A (en) | Composite system power battery with high safety and long service life and preparation method of composite system power battery | |
| JP2022536290A (en) | In-situ polymerized polymer electrolyte for lithium-ion batteries | |
| CN112786832A (en) | Negative plate and lithium ion battery | |
| CN103427113A (en) | Gel polymer electrolyte, polymer battery, and preparation method thereof | |
| CN114765273A (en) | Novel semi-solid battery and preparation method thereof | |
| KR20160114044A (en) | Liquid adhesive coating for coating collector | |
| CN113140731A (en) | All-solid-state lithium battery and preparation method thereof | |
| KR102407600B1 (en) | Binder composition for a non-aqueous secondary battery electrode, a slurry composition for a non-aqueous secondary battery electrode, an electrode for a non-aqueous secondary battery, and a non-aqueous secondary battery | |
| CN108630864A (en) | A kind of cathode and diaphragm integral structure and preparation method thereof and battery | |
| CN108767193B (en) | Positive electrode containing low-swelling graphite coating and lithium battery | |
| CN108767322A (en) | A kind of preparation method of all-solid-state battery core |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200609 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |