CN109216650A - Battery electrode and preparation method thereof and all-solid-state battery - Google Patents
Battery electrode and preparation method thereof and all-solid-state battery Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The present invention relates to all-solid-state battery fields, and in particular to battery electrode and preparation method thereof and all-solid-state battery.The battery electrode includes: the electrode material layer of electrode current collecting body and the attachment of its surface, and the electrode material layer contains polymeric matrix and electrode active material, and the polymeric matrix is cross-linked polymer.Battery electrode and electrolyte layer provided by the invention ionic conductivity with higher and mechanical strength, to make battery that there is preferable specific capacity, cycle life etc..
Description
Technical field
The present invention relates to all-solid-state battery fields, and in particular to battery electrode and preparation method thereof and all-solid-state battery.
Background technique
Lithium ion battery currently on the market is mostly using liquid electrolyte as conductive materials, but in use, liquid
Electrolyte is volatile, inflammable and explosive, leads to many safety problems；And it easily grows Li dendrite, limits lithium metal as negative
The application of pole in the battery.Therefore, it has been proposed that substituting liquid electrolyte with solid polymer electrolyte (SPE).Solid-state is poly-
Polymer electrolyte membrane not only plays a part of ionic conduction, can also prevent the contact of positive and negative electrode.It, can again because its plasticity is strong
Film of different shapes is made according to different needs, flexibility is good, can bear pressure of the electrode in charge and discharge process, high temperature
Stability is good, greatly improves the safety of lithium battery.
CN105680091A discloses a kind of high-performance all-solid lithium-ion battery and preparation method thereof, in this application, adopts
The polymer dielectric modified with lithium superionic conductors improves lithium ion through entire all-solid lithium-ion battery system
Transmission rate improves the rate charge-discharge ability of all-solid lithium-ion battery；However, there are following several big disadvantages for this method: 1.
Cathode pole piece preparation process is complicated, and lithium powder is to environmental requirement height；2. cathode needs to mix in lithium powder and superionic conductors, polymer
It closes, it is difficult to be uniformly mixed, cause pole piece uniformity poor, battery consistency is poor；3. anode, cathode pole piece are needed in polymer electrolytic
It is infiltrated in matter, battery could be made, after infiltration, the polymer dielectric and pole piece of gel state are bonded, and increase lamination process
The difficulty of complexity and correct lamination；4. polymer dielectric ionic conductivity is lower, require gap larger from commercial applications.
CN105489932A discloses a kind of method that UV crosslinking method prepares lithium ionic cell polymer electrolyte film.
The solid electrolyte film is by monomers methyl methacrylate (MMA) UV crosslinking and to be mixed into urethane acrylate (PUA)
It is made with ionic liquid (DEFYTFSI and Py13TFSI), the mechanical strength and ionic conductivity of the dielectric film all obtain one
Determine the raising of degree.But there is also following several big disadvantages for this method: 1. preparation process is complicated, and step is various；2. used in it
The ionic conductivity of polymer P UA and PMMA itself is not high, mainly improves polymer dielectric by the way that ionic liquid is added
The ionic conductivity of film, and ionic liquid higher cost, are not particularly suited for industrial production；3. initiator used in UV crosslinking
Dibenzoyl peroxide property is extremely unstable, and meeting Mingguang City, high temperature and reducing agent has the danger for causing Fire explosion, so behaviour
Risk during work is higher.
Summary of the invention
The purpose of the present invention is to provide a kind of battery electrodes that battery specific capacity is high and preparation method thereof and all solid state electricity
Pond.
To achieve the goals above, one aspect of the present invention provides a kind of battery electrode, and the electrode includes: electrode current collecting body
With the electrode material layer of its surface attachment, the electrode material layer contains polymeric matrix and disperses the electricity in the polymeric matrix
Pole active material, the polymeric matrix are cross-linked polymer；
Wherein, the cross-linked polymer contains the cross-linked structure provided by crosslinking agent and is total to what the cross-linked structure was connect
Polymers chain, the copolymer chain is as containing shown in structural unit shown in structural unit shown in formula (1), formula (2) and formula (3)
The cross-linkable copolymers of structural unit provide, wherein the cross-linkable copolymers pass through structure list shown at least partly formula (3)
It is first to be connect with the crosslinking agent to provide the copolymer chain；
Wherein, R is the alkyl of H or C1-C4, and L is the alkylidene or-R of C0-C41-O-R2, R1For the alkylidene of C0-C4,
R2For the alkylidene of C0-C4；
The crosslinking agent is one of acrylic ester cross-linking agent containing at least two esters of acrylic acid groups or more
Kind, the esters of acrylic acid group is group shown in formula (4) :-O-C (O)-C (R ')=CH2, R ' is the alkyl of H or C1-C4.
Second aspect of the present invention provides a kind of preparation method of battery electrode, this method comprises:
(1) electrode slurry containing electrode active material, cross-linkable copolymers, crosslinking agent and photoinitiator is provided；
(2) electrode slurry of step (1) is coated on electrode current collecting body, and dry, then under ultraviolet light, into
Row crosslinking curing is in forming electrode material layer on electrode current collecting body；
Wherein, the cross-linkable copolymers contain structural unit and formula shown in structural unit shown in formula (1), formula (2)
(3) structural unit shown in；
Wherein, R is the alkyl of H or C1-C4, and L is the alkylidene or-R of C0-C41-O-R2, R1For the alkylidene of C0-C4,
R2For the alkylidene of C0-C4；
The crosslinking agent is one of acrylic ester cross-linking agent containing at least two esters of acrylic acid groups or more
Kind, the esters of acrylic acid group is group shown in formula (4) :-O-C (O)-C (R ')=CH2, R ' is the alkyl of H or C1-C4.
Third aspect present invention provides battery electrode prepared by the above method.
Fourth aspect present invention provides a kind of all-solid-state battery, wherein the all-solid-state battery includes: electrode, electrolyte
Layer and cathode, the anode and/or cathode are above-mentioned battery electrode.
Battery electrode and electrolyte layer provided by the invention ionic conductivity with higher and mechanical strength, to make electricity
Pond has preferable specific capacity, cycle life etc.；Battery manufacturing process greatly simplifies, and manufacturing cost reduces, and ease for operation improves,
Production/manufacture efficiency can be improved with continuous production, high capacity cell can be prepared.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
One aspect of the present invention provides a kind of battery electrode, and the electrode includes: the electricity of electrode current collecting body and the attachment of its surface
Pole material layer, the electrode material layer contains polymeric matrix and disperses the electrode active material in the polymeric matrix, described
Polymeric matrix is cross-linked polymer；
Wherein, the cross-linked polymer contains the cross-linked structure provided by crosslinking agent and is total to what the cross-linked structure was connect
Polymers chain, the copolymer chain is as containing shown in structural unit shown in structural unit shown in formula (1), formula (2) and formula (3)
The cross-linkable copolymers of structural unit provide, wherein the cross-linkable copolymers pass through structure list shown at least partly formula (3)
It is first to be connect with the crosslinking agent to provide the copolymer chain；
Wherein, R is the alkyl of H or C1-C4, and L is the alkylidene or-R of C0-C41-O-R2, R1For the alkylidene of C0-C4,
R2For the alkylidene of C0-C4；
The crosslinking agent is one of acrylic ester cross-linking agent containing at least two esters of acrylic acid groups or more
Kind, the esters of acrylic acid group is group shown in formula (4) :-O-C (O)-C (R ')=CH2, R ' is the alkyl of H or C1-C4.
According to the present invention, in the cross-linked polymer, the formula (3) of the double bond of the crosslinking agent and the cross-linkable copolymers
Shown in the double bond of structural unit cause polymerization, and multiple double bonds of a molecule cross-link agent can be with a cross-linkable copolymers
Multiple formulas (3) shown in structural unit double bond bonding, or structure list shown in formula (3) with multiple cross-linkable copolymers
The double bond of structural unit shown in the double bond bonding of member or multiple formulas (3) of a cross-linkable copolymers can be with multiple crosslinkings
The double bond of agent is bonded, and the cross-linked polymer of tridimensional network is consequently formed.Such cross-linked polymer is as polymeric matrix
When, it can be improved ionic conductivity and mechanical strength.
In the present invention, the specific example of the alkyl of C1-C4 can be for example methyl, ethyl, n-propyl, isopropyl, just
Butyl, isobutyl group, sec-butyl or tert-butyl.
The specific example of the alkylidene of C0-C4 for example can be the alkylidene ,-CH of C02-、-CH2CH2-、-
CH2CH2CH2-、-CH(CH3)CH2-、-CH2CH(CH3)-、-CH2CH2CH2CH2Etc..Wherein, the alkylidene of the C0 refers to and does not deposit
Or be connecting key, i.e. the group on the group both sides will be directly connected to.
Preferably, R H, methyl or ethyl, L are the alkylidene ,-CH of C02-、-CH2CH2-、-CH2CH2CH2-、-O-、-O-
CH2-、-O-CH2CH2-、-CH2-O-、-CH2-O-CH2-、-CH2-O-CH2CH2-、-CH2CH2-O-、-CH2CH2-O-CH2Or-
CH2CH2-O-CH2CH2-；R ' is H, methyl or ethyl.
According to the present invention, in the cross-linkable copolymers, structural unit shown in formula (1), structural unit shown in formula (2)
Can be changed in a wider range with the molar ratio of structural unit shown in formula (3), preferably structural unit shown in formula (1),
The molar ratio of structural unit shown in structural unit shown in formula (2) and formula (3) is 100:0.5-25:0.5-20, preferably
100:1-21:0.5-15, more preferably 100:1-15:1-10 are still more preferably 100:1-8:1-6.Most preferred real
It applies in mode, structural unit shown in structural unit structural units as shown in formula (1) of the cross-linkable copolymers, formula (2)
It is constituted with structural unit shown in formula (3).And the cross-linkable copolymers are preferably the structural unit as shown in formula (1), formula (2)
Shown in the linear random copolymer that constitutes of structural unit shown in structural unit and formula (3).
According to the present invention, the weight average molecular weight of the cross-linkable copolymers can change in a wider range, it is preferable that institute
The weight average molecular weight for stating cross-linkable copolymers is 5,000-5,000,000g/mol, preferably 50,000-1,000,000g/mol,
More preferably 50,000-500,000g/mol are still more preferably 50,000-95,000g/mol, for example, 60,000-95,
000g/mol。
According to the present invention, the crosslinking agent is in the acrylic ester cross-linking agent containing at least two esters of acrylic acid groups
It is one or more, the esters of acrylic acid group of group shown in the formula (4) can be acrylate group, methacrylate
Group etc..The crosslinking agent used in the present invention is small molecule crosslinking agent, it is preferable that the crosslinking agent is dimethacrylate second
Diol ester, ethylene glycol diacrylate, dimethacrylate, diethylene glycol diacrylate, triethylene glycol two
Methacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethylacrylate, tetraethylene glycol diacrylate, two
Methacrylic acid -1,3- propylene glycol ester, dimethacrylate -1,2- propylene glycol ester, diacrylate -1,3- propylene glycol ester, dipropyl
Olefin(e) acid -1,2- propylene glycol ester, dimethacrylate -1,4- butanediol ester, dimethacrylate -1,3 butylene glycol ester, two propylene
Acid -1,4- butanediol ester, diacrylate -1,3 butylene glycol ester, pentaerythritol diacrylate, pentaerythritol triacrylate and
One of pentaerythritol tetraacrylate is a variety of, more preferably triethylene glycol dimethacrylate, triethylene glycol dipropyl
One of olefin(e) acid ester, pentaerythritol triacrylate and pentaerythritol tetraacrylate are a variety of.
According to the present invention, the content for the cross-linked structure unit that the crosslinking agent provides depends on required cross-linked polymer
The degree of cross linking, it is preferable that on the basis of the weight of the polymeric matrix, the content of the copolymer chain is 60-95 weight %, excellent
It is selected as 70-92 weight %, more preferably 70-90 weight %, for example, 72-80 weight %.Preferably, the cross-linked structure contains
Amount is 5-40 weight %, preferably 8-30 weight %, more preferably 20-30 weight %, for example, 21-25 weight %.
According to the present invention, the consumption proportion of the electrode active material and polymeric matrix can become in a wider range
It is dynamic, it is preferable that relative to the electrode active material of 100 parts by weight, the content of the polymeric matrix is 5-100 parts by weight, excellent
It is selected as 10-80 parts by weight, more preferably 20-50 parts by weight.
In a preferred embodiment of the invention, the electrode active material relative to 100 parts by weight, the polymerization
In object matrix, the content of the structure division provided by cross-linkable copolymers is 5-70 parts by weight, the structural portion provided by crosslinking agent
The content divided is 1-20 parts by weight.Preferably, the content of the structure division provided by cross-linkable copolymers is 10-60 parts by weight,
The content of the structure division provided by crosslinking agent is 2-15 parts by weight.It is highly preferred that the structural portion provided by cross-linkable copolymers
The content divided is 20-30 parts by weight (for example, 25-29 parts by weight), and the content of the structure division provided by crosslinking agent is 4-12 weight
It measures part (for example, 6-8 parts by weight).
Wherein, the electrode can be anode, be also possible to cathode, when the electrode is for anode, the electrode activity
Material is positive electrode active materials, and the electrode material layer of formation is positive electrode material layer；When the electrode is cathode, the electrode active
Property material be negative electrode active material, the electrode material layer of formation is negative electrode material layer, and the electrode active material is negative electrode material
Layer.
When the electrode material layer is positive electrode material layer, the electrode obtained is anode, wherein the positive electrode active materials
Specific type is not limited specifically, is conventional raw material, can be selected according to demand.For example, the positive-active
Material includes but is not limited to cobalt acid lithium (LiCoO2), LiMn2O4 (LiMn2O4), manganous acid lithium, ternary material (lithium transition-metal oxygen
Compound) and LiFePO4 (LiFePO4) one of or it is a variety of.
According to the present invention, when the electrode material layer is positive electrode material layer, the positive electrode material layer can also contain lithium
Salt, conductive agent and binder.Preferably, the positive electrode active materials relative to 100 parts by weight, the content of the lithium salts are 1-20 weight
Measure part, preferably 5-15 parts by weight；The content of the conductive agent is 5-20 parts by weight, preferably 6-15 parts by weight；The bonding
The content of agent is 1-20 parts by weight, preferably 2-15 parts by weight.
Wherein, the specific type of the lithium salts, conductive agent and binder is not limited specifically, is conventional original
Material, can be selected according to demand.
For example, the lithium salts is LiClO4(lithium perchlorate), LiPF6(lithium hexafluoro phosphate), LiBF4(LiBF4),
LiBOB (dioxalic acid lithium borate), LiN (SO2CF3)2(double trifluoro (methane sulfonic acid) imine lithiums), LiCF3SO3(trifluoromethane sulfonic acid
Lithium) and LiN (SO2CF2CF3)2One of or it is a variety of.
For example, superconduction carbon, conductive carbon black, electrically conductive graphite, carbon nanotube, graphene and carbon nanometer can be selected in the conductive agent
One of fiber is a variety of.
For example, Kynoar (PVDF), butadiene-styrene rubber (SBR) and sodium carboxymethylcellulose (CMC) can be selected in binder
One of or it is a variety of.
When the electrode material layer is negative electrode material layer, the electrode obtained is cathode, wherein the negative electrode active material
Specific type is not limited specifically, is conventional raw material, can be selected according to demand.For example, the negative electrode active
Material includes but is not limited to one of graphite, active carbon, graphene, carbon nanotube, silicon, Si-C composite material etc. or a variety of.
According to the present invention, when the electrode material layer is negative electrode material layer, the negative electrode material layer can also contain lithium
Salt, binder and thickener.Preferably, the negative electrode active material relative to 100 parts by weight, the content of the lithium salts are 1-20 weight
Measure part, preferably 1-5 parts by weight；The content of the binder is 1-20 parts by weight, preferably 1-5 parts by weight；The thickener
Content be 1-20 parts by weight, preferably 1-5 parts by weight.
Wherein, the specific type of the lithium salts, binder and thickener is not limited specifically, is conventional original
Material, can be selected according to demand.
Wherein, the lithium salts and binder are as described above.
One of methylcellulose, carboxymethyl cellulose etc. or a variety of can be selected in the thickener.
In accordance with the present invention it is preferred that the electrode material layer with a thickness of 10-100 μm (single side thickness).
According to the present invention, there is no any special restriction to the electrode current collecting body, the electricity of this field routine can be used
Pole collector, for example, copper foil, aluminium foil etc., thickness for example can be 1-100 μm.
Second aspect of the present invention provides a kind of preparation method of battery electrode, this method comprises:
(1) electrode slurry containing electrode active material, cross-linkable copolymers, crosslinking agent and photoinitiator is provided；
(2) electrode slurry of step (1) is coated on electrode current collecting body, and dry, then under ultraviolet light, into
Row crosslinking curing is in forming electrode material layer on electrode current collecting body；
Wherein, the cross-linkable copolymers contain structural unit and formula shown in structural unit shown in formula (1), formula (2)
(3) structural unit shown in；
Wherein, R is the alkyl of H or C1-C4, and L is the alkylidene or-R of C0-C41-O-R2, R1For the alkylidene of C0-C4,
R2For the alkylidene of C0-C4；
The crosslinking agent is one of acrylic ester cross-linking agent containing at least two esters of acrylic acid groups or more
Kind, the esters of acrylic acid group is group shown in formula (4) :-O-C (O)-C (R ')=CH2, R ' is the alkyl of H or C1-C4.
According to the present invention, the group of above-mentioned cross-linkable copolymers and type selection, the group of crosslinking agent and type select such as
Described above, details are not described herein by the present invention.
According to the present invention, the method that the cross-linkable copolymers can be this field routine is made, and is also possible to commercially available product
According to the present invention, there is no particular limitation to this by the present invention.
The dosage of the cross-linkable copolymers and crosslinking agent can be according to institute respective in the cross-linked polymer being outlined above
The content accounted for is selected, it is preferable that described cross-linking total on the basis of the total weight of the cross-linkable copolymers and crosslinking agent
The dosage of polymers is 60-95 weight %, preferably 70-92 weight %, more preferably 70-90 weight %, for example, 72-80 weight
Measure %.Preferably, the dosage of the crosslinking agent is 5-40 weight %, preferably 8-30 weight %, more preferably 20-30 weight
Measure %, for example, 21-25 weight %.
In accordance with the present invention it is preferred that the electrode active material relative to 100 parts by weight, the cross-linkable copolymers
Total dosage with crosslinking agent is 5-100 parts by weight, preferably 10-80 parts by weight, more preferably 20-50 parts by weight.
In accordance with the present invention it is preferred that the photoinitiator is 2- hydroxy-2-methyl propiophenone, (2,4,6- trimethylbenzene first
Acyl group) phosphinic acid ethyl ester, 4- dimethylaminobenzoic acid ethyl ester, 1- hydroxycyclohexyl phenyl ketone, benzoin dimethylether, o-benzoyl
One of methyl benzoate and 4- chlorobenzophenone are a variety of.The dosage of the photoinitiator can become in a wider range
It is dynamic, it is preferable that using the total weight of the cross-linkable copolymers, crosslinking agent and silane coupler modified inorganic nano-particle as base
Standard, the dosage of the photoinitiator are 2-15 weight %, preferably 3-8 weight %.
According to the present invention, when the electrode of preparation is anode, the electrode material layer is negative electrode material layer, the electrode active
Property material is then positive electrode active materials.The electrode slurry may be incorporated into lithium salts, conductive agent and binder.Preferably, phase
For the positive electrode active materials of 100 parts by weight, the content of the lithium salts is 1-20 parts by weight, preferably 5-15 parts by weight；It is described
The content of conductive agent is 5-50 parts by weight, preferably 6-20 parts by weight；The content of the binder is 1-20 parts by weight, preferably
2-15 parts by weight.Wherein, the lithium salts, conductive agent and binder are as defined in above, and details are not described herein by the present invention.
According to the present invention, when the electrode of preparation is cathode, the electrode material layer is negative electrode material layer, the electrode active
Property material be negative electrode active material, the electrode slurry, which also introduces, lithium salts, binder and thickener.Preferably, relative to 100
The negative electrode active material of parts by weight, the content of the lithium salts are 1-20 parts by weight, preferably 1-5 parts by weight；The binder
Content is 1-20 parts by weight, preferably 1-5 parts by weight；The content of the thickener is 1-20 parts by weight, preferably 1-5 weight
Part.Wherein, the lithium salts, binder and thickener are as defined in above, and details are not described herein by the present invention.
According to the present invention, the electrode slurry further includes the dispersion solvent used, which for example can be N, N-
Dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, dimethyl sulfoxide, tetrahydrofuran, chloroform, methylene chloride
With one of acetonitrile or a variety of.The dosage of the dispersion solvent can change in a wider range, it is preferable that relative to 100 weights
Measure the electrode active material of part, the dosage of the dispersion solvent is 10-1000 parts by weight, preferably 20-800 parts by weight, more excellent
It is selected as 100-500 parts by weight, for example, 200-400 parts by weight.
According to the present invention, in the preparation method of above-mentioned battery electrode, electrode slurry is coated on electrode current collecting body by step (2)
On, and drying forms half dry film on a current collector, can then be formed on a current collector by ultraviolet light crosslinking curing again
Electrode material layer.Wherein, which can be carried out using the ultraviolet irradiation mode of this field routine, the present invention to this simultaneously
It is limited without special.The time of the crosslinking curing is 30s-15min, preferably 2-10min.
According to the present invention, by the above method, transparent cross-linked polymer film can be formed (i.e. on electrode current collecting body surface
Electrode material layer), this method can also include the resulting collector for being attached with electrode material layer of step (2) is dried with
Remaining solvent and moisture etc. are removed, such as the dry 10-30h at 40-80 DEG C.
After above-mentioned electrode material layer is formed, same electricity can be formed in the same way in the another side of electrode current collecting body
Pole material layer, to be formed two-sided all with the battery electrode of electrode material layer of the invention.
Third aspect present invention provides battery electrode prepared by the above method.
Fourth aspect present invention provides a kind of all-solid-state battery, wherein the all-solid-state battery includes: electrode, electrolyte
Layer and cathode, the anode and/or cathode are above-mentioned battery electrode.
According to the present invention, the electrolyte layer is preferably specifically-built, and the electrolyte layer is positive and/or negative to be attached to
Polymer dielectric film on extremely, the polymer dielectric film contain polymeric matrix and are scattered in the polymeric matrix
Lithium salts.The polymeric matrix and lithium salts are as described above.
In accordance with the present invention it is preferred that the content of the lithium salts is 10- on the basis of the total weight of the polymeric matrix
30 weight %, preferably 15-27 weight %, more preferably 18-22 weight %.
According to the present invention, in another preferred embodiment, the electrolyte layer is to be attached to anode and/or cathode
On polymer dielectric film, the preparation method of the polymer dielectric film includes:
(a) electrolyte slurry containing lithium salts, cross-linkable copolymers, crosslinking agent and photoinitiator is provided；
(b) electrolyte slurry is coated on the anode and/or cathode, and dry, then in ultraviolet light
Under, carry out crosslinking curing in anode and/or cathode on form electrolyte layer；
Wherein, the cross-linkable copolymers, crosslinking agent and photoinitiator are for example described above.
According to the present invention, the organic solvent that the electrolyte slurry uses for example can be n,N-Dimethylformamide, N,
One of N- dimethyl acetamide, N-Methyl pyrrolidone, dimethyl sulfoxide, tetrahydrofuran, chloroform, methylene chloride and acetonitrile or
It is a variety of.The dosage of the organic solvent can change in a wider range, it is preferable that the cross-linking copolymerization relative to 100 parts by weight
Object, the dosage of the organic solvent are 20-100 parts by weight, preferably 30-80 parts by weight.
The crosslinking curing above described in, which can also include being attached with electricity for step (b) is resulting
The anode and/or cathode for solving matter layer are dried to remove remaining solvent and moisture etc., such as the dry 10- at 40-80 DEG C
30h。
After above-mentioned electrolyte layer is formed, it can be formed in the same way similarly in the another side of anode and/or cathode
Electrolyte layer, to be formed two-sided all with the anode and/or cathode of electrolyte layer of the invention.Wherein, two-sided formation electrolysis
After matter layer, it can also carry out hot pressing (such as hot pressing at 50-70 DEG C), it is strong with the combination for improving electrolyte layer and battery electrode
Degree.
According to the present invention, the thickness of the electrolyte layer for example can be 10-200 μm (single side thickness).
According to the present invention, the cathode of above-mentioned battery may be the cathode of this field routine, such as can adhere to for surface
There is the negative current collector of lithium metal.The negative current collector can be for example copper foil, copper mesh etc..
In accordance with the present invention it is preferred that the anode and cathode are all the resulting corresponding anode of the present invention and cathode.
According to the present invention, above-mentioned all-solid-state battery can be after anode and the upper tab of cathode welding, and overlapping is placed in aluminium
Pressure is sealed in plastic film, can be obtained.
Battery of the invention especially and under the cooperation of above-mentioned electrolyte layer, can obtained higher using above-mentioned battery electrode
Specific capacity, cycle life etc..
The present invention will be described in detail by way of examples below.
In following example:
Cross-linkable copolymers 1# is purchased from the bright copolymer at chemical company, is structural unit, formula as shown in formula (1)
(2) structural unit (R=H, L=-CH shown in structural unit and formula shown in (3)2-O-CH2) composition random copolymer,
In, structural unit shown in formula (1), structural unit shown in structural unit and formula (3) shown in formula (2) molar ratio be 93:
6:1, weight average molecular weight 95,000g/mol.
Cross-linkable copolymers 2# is purchased from the bright copolymer at chemical company, is structural unit, formula as shown in formula (1)
(2) structural unit (R=H, L=-CH shown in structural unit and formula shown in (3)2-O-CH2) composition random copolymer,
In, structural unit shown in formula (1), structural unit shown in structural unit and formula (3) shown in formula (2) molar ratio be 96:
1:3, weight average molecular weight 80,000g/mol.
Cross-linkable copolymers 3# is purchased from the bright copolymer at chemical company, is structural unit, formula as shown in formula (1)
(2) structural unit (R=H, L=-CH shown in structural unit and formula shown in (3)2-O-CH2) composition random copolymer,
In, structural unit shown in formula (1), structural unit shown in structural unit and formula (3) shown in formula (2) molar ratio be 90:
5:5, weight average molecular weight 70,000g/mol.
Cross-linkable copolymers 4# is purchased from the bright copolymer at chemical company, is structural unit, formula as shown in formula (1)
(2) structural unit (R=H, L=-CH shown in structural unit and formula shown in (3)2-O-CH2) composition random copolymer,
In, structural unit shown in formula (1), structural unit shown in structural unit and formula (3) shown in formula (2) molar ratio be 93:
6:1, weight average molecular weight 50,000g/mol.
Cross-linkable copolymers 5# is purchased from the bright copolymer at chemical company, is structural unit, formula as shown in formula (1)
(2) structural unit (R=H, L=-CH shown in structural unit and formula shown in (3)2-O-CH2) composition random copolymer,
In, structural unit shown in formula (1), structural unit shown in structural unit and formula (3) shown in formula (2) molar ratio be 93:
6:1, weight average molecular weight 200,000g/mol.
Cross-linkable copolymers 6# is purchased from the bright copolymer at chemical company, is structural unit, formula as shown in formula (1)
(2) structural unit (R=H, L=-CH shown in structural unit and formula shown in (3)2-O-CH2) composition random copolymer,
In, structural unit shown in formula (1), structural unit shown in structural unit and formula (3) shown in formula (2) molar ratio be 93:
6:1, weight average molecular weight 40,000g/mol.
Copolymer 7# is purchased from the bright copolymer at chemical company, for the structural unit as shown in formula (1) and formula (2) institute
The random copolymer of the structural unit composition shown, wherein structural unit shown in structural unit shown in formula (1) and formula (2)
Molar ratio is 12:1, weight average molecular weight 95,000g/mol.
Kynoar: being commercially available from the product of Aladdin Industrial Co., and weight average molecular weight is 1.5 × 105~5
×105g/mol。
PEO: the product of Aladdin IndustrialCo., weight average molecular weight 10 are commercially available from5~5 × 106g/mol。
Embodiment 1
The present embodiment is for illustrating anode of the invention and preparation method thereof and all-solid-state battery.
Prepare battery anode slice:
(1) by the positive electrode LiFePO of 50 parts by weight4, the cross-linkable copolymers 1# of 12.5 parts by weight, 6.1 parts by weight
LiN(SO2CF2CF3)2, the pentaerythritol tetraacrylates of 5.2 parts by weight, the 2- hydroxy-2-methyl Propafenone of 1.2 parts by weight, 5
The Kynoar of parts by weight and the electrically conductive graphite of 5 parts by weight are scattered in the N-Methyl pyrrolidone solvent of 200 parts by weight, are obtained
To anode sizing agent；
(2) by anode sizing agent be coated on aluminium foil (with a thickness of 20 μm) it is two-sided on, then 60 DEG C of dry 1h are solidified with ultraviolet light
Instrument irradiates 5min, continues thereafter with 60 DEG C of dryings for 24 hours, and battery anode slice, the positive electrode material layer that anode sizing agent is formed is made in roll-in
With a thickness of 50 μm (single side thickness).
Form electrolyte layer:
(1) by the cross-linkable copolymers 1# of 50 parts by weight, the LiN (SO of 20 parts by weight2CF2CF3)2, 20 parts by weight season penta
Tetra-acrylate and the 2- hydroxy-2-methyl Propafenone of 4.8 parts by weight are scattered in the N-Methyl pyrrolidone of 25 parts by weight
In solvent, electrolyte slurry is obtained；
(2) electrolyte slurry is coated in the one side of above-mentioned battery anode slice, the dry 1h at 60 DEG C, then with purple
Outer Photocureable instrument irradiates 5min, makes its film-forming to form electrolyte layer, then proceedes to 60 DEG C of dryings for 24 hours, use after having dried
Same method forms same electrolyte layer in battery anode slice reverse side, and the hot pressing at 60 DEG C is obtaining being attached with electrolyte layer just
Pole, electrolyte layer with a thickness of 50 μm (single side thickness).
Battery assembly:
In the glove box containing high-purity Ar atmosphere, by the above-mentioned anode for being attached with electrolyte layer and lithium copper foil slice is covered
(cathode, the same below), and with mash welder soldering polar ear, then anode and cathode lamination are placed in aluminum plastic film and sealed, after taking-up
The hot pressing 1h at 60 DEG C；Thus battery C1 is made.
Embodiment 2
The present embodiment is for illustrating anode of the invention and preparation method thereof and all-solid-state battery.
Prepare battery anode slice:
(1) by the positive electrode LiCoO of 60 parts by weight2, the cross-linkable copolymers 2# of 15 parts by weight, 4.88 amount parts LiN
(SO2CF2CF3)2, the pentaerythritol tetraacrylates of 4.16 parts by weight, the 4- dimethylaminobenzoic acid ethyl ester of 0.96 parts by weight, 4
The Kynoar of parts by weight and the conductive carbon black of 5 parts by weight are scattered in the n,N-Dimethylformamide solvent of 240 parts by weight,
Obtain anode sizing agent；
(2) by anode sizing agent be coated on aluminium foil (with a thickness of 20 μm) it is two-sided on, then 60 DEG C of dry 1h are solidified with ultraviolet light
Instrument irradiates 10min, continues thereafter with 60 DEG C of dryings for 24 hours, and battery anode slice, the positive electrode material layer that anode sizing agent is formed is made in roll-in
With a thickness of 30 μm (single side thickness).
Form electrolyte layer:
(1) by the cross-linkable copolymers 2# of 50 parts by weight, the LiN (SO of 15 parts by weight2CF2CF3)2, 13.8 parts by weight season
Penta tetra-acrylate and the 4- dimethylaminobenzoic acid ethyl ester of 3.2 parts by weight are scattered in the N of 30 parts by weight, N- dimethyl methyl
In amide solvent, electrolyte slurry is obtained；
(2) electrolyte slurry is coated in the one side of above-mentioned battery anode slice, the dry 1h at 60 DEG C, then with purple
Outer Photocureable instrument irradiates 10min, makes its film-forming to form electrolyte layer, then proceedes to 60 DEG C of dryings for 24 hours, use after having dried
Same method forms same electrolyte layer in battery anode slice reverse side, and the hot pressing at 60 DEG C is obtaining being attached with electrolyte layer just
Pole, electrolyte layer with a thickness of 30 μm (single side thickness).
Battery assembly:
In the glove box containing high-purity Ar atmosphere, by the above-mentioned anode for being attached with electrolyte layer and lithium copper foil slice is covered,
And with mash welder soldering polar ears, then anode and cathode lamination are placed in aluminum plastic film and sealed, after taking-up at 60 DEG C hot pressing 1h；
Thus battery C2 is made.
Embodiment 3
The present embodiment is for illustrating anode of the invention and preparation method thereof and all-solid-state battery.
Prepare battery anode slice:
(1) by the positive electrode LiCoO of 70 parts by weight2, the cross-linkable copolymers 3# of 20 parts by weight, 3.66 amount parts
LiBOB, the pentaerythritol tetraacrylate of 6.12 parts by weight, the 2- hydroxy-2-methyl Propafenone of 1.72 parts by weight, 3 parts by weight
Kynoar and the electrically conductive graphites of 6 parts by weight be scattered in the acetonitrile solvent of 280 parts by weight, obtain anode sizing agent；
(2) by anode sizing agent be coated on aluminium foil (with a thickness of 20 μm) it is two-sided on, then 60 DEG C of dry 1h are solidified with ultraviolet light
Instrument irradiates 6min, continues thereafter with 60 DEG C of dryings for 24 hours, and battery anode slice, the positive electrode material layer that anode sizing agent is formed is made in roll-in
With a thickness of 20 μm (single side thickness).
Form electrolyte layer:
(1) by the cross-linkable copolymers 3# of 50 parts by weight, the LiBOB of 12 parts by weight, 15.3 parts by weight pentaerythrite four
Acrylate and the 4- dimethylaminobenzoic acid ethyl ester of 4.3 parts by weight are scattered in the acetonitrile solvent of 30 parts by weight, are electrolysed
Chylema material；
(2) electrolyte slurry is coated in the one side of above-mentioned battery anode slice, the dry 1h at 60 DEG C, then with purple
Outer Photocureable instrument irradiates 6min, makes its film-forming to form electrolyte layer, then proceedes to 60 DEG C of dryings for 24 hours, use after having dried
Same method forms same electrolyte layer in battery anode slice reverse side, and the hot pressing at 60 DEG C is obtaining being attached with electrolyte layer just
Pole, electrolyte layer with a thickness of 20 μm (single side thickness).
Battery assembly:
In the glove box containing high-purity Ar atmosphere, by the above-mentioned anode for being attached with electrolyte layer and lithium copper foil slice is covered,
And with mash welder soldering polar ears, then anode and cathode lamination are placed in aluminum plastic film and sealed, after taking-up at 60 DEG C hot pressing 1h；
Thus battery C3 is made.
Embodiment 4
The present embodiment is for illustrating battery cathode of the invention and preparation method thereof and all-solid-state battery.
According to method described in embodiment 1, the difference is that:
Prepare battery cathode sheet:
(1) by the graphite of 80 parts by weight, the cross-linkable copolymers 1# of 7.9 parts by weight, 3.9 parts by weight LiN
(SO2CF2CF3)2, the pentaerythritol tetraacrylates of 3.4 parts by weight, the 2- hydroxy-2-methyl Propafenone of 0.8 parts by weight, 2.4
The butadiene-styrene rubber of parts by weight and the carboxymethyl cellulose of 1.6 parts by weight are scattered in the N-Methyl pyrrolidone solvent of 320 parts by weight
In, obtain negative electrode slurry；
(2) by negative electrode slurry be coated on copper foil (with a thickness of 20 μm) it is two-sided on, then 60 DEG C of dry 1h are solidified with ultraviolet light
Instrument irradiates 5min, continues thereafter with 60 DEG C of dryings for 24 hours, and battery cathode sheet, the negative electrode material layer that negative electrode slurry is formed is made in roll-in
With a thickness of 50 μm (single side thickness).
Thus battery C4 is made.
Embodiment 5
The present embodiment is for illustrating anode of the invention and preparation method thereof and all-solid-state battery.
According to method described in embodiment 1, the difference is that:
Prepare battery anode slice: positive electrode LiFePO4Dosage be 50 parts by weight, the dosage of cross-linkable copolymers 1# is
5 parts by weight, the dosage of pentaerythritol tetraacrylate are 2.1 parts by weight, and the dosage of 2- hydroxy-2-methyl Propafenone is 0.65 weight
Measure part.
Finally obtained battery C5.
Embodiment 6
The present embodiment is for illustrating anode of the invention and preparation method thereof and all-solid-state battery.
According to method described in embodiment 1, the difference is that:
Prepare battery anode slice: positive electrode LiFePO4Dosage be 50 parts by weight, the dosage of cross-linkable copolymers 1# is
25 parts by weight, the dosage of pentaerythritol tetraacrylate are 7.5 parts by weight, and the dosage of 2- hydroxy-2-methyl Propafenone is 2 weight
Part.
Finally obtained battery C6.
Embodiment 7-9
The present embodiment is for illustrating anode of the invention and preparation method thereof and all-solid-state battery.
According to method described in embodiment 1, unlike, prepare battery anode slice and formed in electrolyte layer, using point
Not Cai Yong cross-linkable copolymers 4#, 5# and 6# replace cross-linkable copolymers 1#, thus respectively be made battery C7, C8 and C9.
Comparative example 1
Prepare battery anode slice:
(1) by the positive electrode LiFePO of 50 parts by weight4, the PEO of 20 parts by weight, 6.1 parts by weight LiN
(SO2CF2CF3)2, the Kynoar of 20 parts by weight and the electrically conductive graphite of 5 parts by weight be scattered in the N- methyl pyrroles of 200 parts by weight
In pyrrolidone solvent, anode sizing agent is obtained；
(2) by anode sizing agent be coated on aluminium foil (with a thickness of 20 μm) it is two-sided on, for 24 hours, and battery is made in roll-in for 60 DEG C of dryings
Positive plate, the positive electrode material layer that anode sizing agent is formed is with a thickness of 50 μm (single side thickness).
Form electrolyte layer:
(1) by the LiN (SO of the PEO of 40 parts by weight and 10 parts by weight2CF2CF3)2It is scattered in the N- methyl pyrrole of 30 parts by weight
In pyrrolidone solvent, electrolyte slurry is obtained；
(2) electrolyte slurry is coated in the one side of above-mentioned battery anode slice, for 24 hours in 60 DEG C of dryings, after having dried
Same electrolyte layer is formed in battery anode slice reverse side with same method, the hot pressing at 60 DEG C obtains being attached with electrolyte layer
Anode, electrolyte layer with a thickness of 50 μm (single side thickness).
Battery assembly:
In the glove box containing high-purity Ar atmosphere, by the above-mentioned anode for being attached with electrolyte layer and lithium copper foil slice is covered,
And with mash welder soldering polar ears, then anode and cathode lamination are placed in aluminum plastic film and sealed, after taking-up at 60 DEG C hot pressing 1h；
Thus battery DC1 is made.
Comparative example 2
According to method described in embodiment 1, the difference is that, it prepares battery anode slice and is formed in electrolyte layer, using altogether
Polymers 7# replaces cross-linkable copolymers 1#, obtains corresponding battery anode slice and battery DC2.
Test case 1
Peel strength and compacted density and the specific capacity of resulting battery to the battery electrode piece in above-mentioned example into
Row test, the results are shown in Table 1, in which:
Electrode slice peel strength test: using the universal testing machine of the WDW-0.5 of Shenzhen Jun Rui test apparatus Co., Ltd
It is tested, is specifically included: electrode slice being cut into the long generous sample for being 60 × 20mm, its back side is sticked to test with adhesive tape
On stainless steel plate A, reverse side pastes 18mm wide adhesive tape, and adhesive tape exposes a part, and adhesive tape is sticked on stainless steel plate B, will not
Rust steel plate A, B are clipped on testing machine, strong with the velocity test removing of 30mm/min under the conditions of 25 DEG C, relative humidity < 5%RH
Degree.
Electrode compacted density test: using Shenzhen Jun Rui test apparatus Co., Ltd WDW-0.5 universal testing machine into
Row test, specifically includes: distinguishing measuring electrode sheet and aluminum foil thickness with digimatic micrometer, is denoted as L (μm), electrode is cut into
The disk of 13mm diameter weighs its quality, is denoted as m (mg)；Compacted density is denoted as ρ, ρ=m × 10-3/(3.14×(1.3/2)2
×L×10-4)=7.54m/L g/cm3。
Specific capacity test: right using blue electric battery test system (CT2001C, Wuhan Land Electronic Co., Ltd.)
Battery carries out charge-discharge test, and detailed process includes: to carry out constant current charge and discharge to lithium ion battery using charge and discharge instrument at 60 DEG C
Power mode test, wherein charge cutoff voltage 4.0V, discharge cut-off voltage 3.0V, charge-discharge magnification 0.5C are tested
20 specific capacities of specific capacity for the first time and circulation of each lithium ion battery arrived.
Table 1
It can be seen from Table 1 that the resulting electrode slice of present invention strength of glass with higher and compacted density, are suitable for using
Make the electrode slice of lithium battery, and resulting battery also specific capacity with higher, and has extended cycle life.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (15)
1. a kind of battery electrode, which is characterized in that the electrode includes: the electrode material of electrode current collecting body and the attachment of its surface
Layer, the electrode material layer contain polymeric matrix and electrode active material, and the polymeric matrix is cross-linked polymer；
Wherein, the cross-linked polymer contains the cross-linked structure provided by crosslinking agent and the copolymer connecting with the cross-linked structure
Chain, the copolymer chain is as containing structure shown in structural unit shown in structural unit shown in formula (1), formula (2) and formula (3)
The cross-linkable copolymers of unit provide, wherein the cross-linkable copolymers by structural unit shown at least partly formula (3) with
The crosslinking agent connection is to provide the copolymer chain；
Formula (1):Formula (2):Formula (3):
Wherein, R is the alkyl of H or C1-C4, and L is the alkylidene or-R of C0-C41-O-R2, R1For the alkylidene of C0-C4, R2For
The alkylidene of C0-C4；
The crosslinking agent is one of acrylic ester cross-linking agent containing at least two esters of acrylic acid groups or a variety of, institute
Stating esters of acrylic acid group is group shown in formula (4) :-O-C (O)-C (R ')=CH2, R ' is the alkyl of H or C1-C4.
2. battery electrode according to claim 1, wherein R H, methyl or ethyl, L are the alkylidene ,-CH of C02-、-
CH2CH2-、-CH2CH2CH2-、-O-、-O-CH2-、-O-CH2CH2-、-CH2-O-、-CH2-O-CH2-、-CH2-O-CH2CH2-、-
CH2CH2-O-、-CH2CH2-O-CH2Or-CH2CH2-O-CH2CH2-；R ' is H, methyl or ethyl；
Preferably, in the cross-linkable copolymers, structural unit shown in formula (1), structural unit and formula (3) shown in formula (2)
Shown in structural unit molar ratio be 100:0.5-25:0.5-20, preferably 100:1-21:0.5-15, more preferably 100:
1-15:1-10 is still more preferably 100:1-8:1-6；
Preferably, the weight average molecular weight of the cross-linkable copolymers is 5,000-5,000,000g/mol, preferably 50,000-1,
000,000g/mol, more preferably 50,000-500,000g/mol are still more preferably 50,000-95,000g/mol.
3. battery electrode according to claim 1 or 2, wherein described total on the basis of the weight of the polymeric matrix
The content of polymers chain is 60-95 weight %, preferably 70-92 weight %, more preferably 70-90 weight %；The cross-linked structure
Content be 5-40 weight %, preferably 8-30 weight %；
Preferably, the crosslinking agent is ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethyl propylene
Olefin(e) acid ester, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol
Dimethylacrylate, tetraethylene glycol diacrylate, dimethacrylate -1,3- propylene glycol ester, dimethacrylate -1,2-
Propylene glycol ester, diacrylate -1,3- propylene glycol ester, diacrylate -1,2- propylene glycol ester, dimethacrylate -1,4- butanediol
Ester, dimethacrylate -1,3 butylene glycol ester, diacrylate -1,4- butanediol ester, diacrylate -1,3 butylene glycol ester, season penta
One of tetrol diacrylate, pentaerythritol triacrylate and pentaerythritol tetraacrylate are a variety of, more preferably
Triethylene glycol dimethacrylate, triethylene glycol diacrylate, pentaerythritol triacrylate and pentaerythrite tetrapropylene
One of acid esters is a variety of.
4. battery electrode according to claim 1 or 2, wherein relative to the electrode material of 100 parts by weight, the polymerization
The content of object matrix is 5-100 parts by weight, preferably 10-80 parts by weight, more preferably 20-50 parts by weight；
Preferably, the electrode material layer is positive electrode material layer, and the electrode active material is positive electrode active materials, the anode
Material layer also contains lithium salts, conductive agent and binder；Relative to the positive electrode active materials of 100 parts by weight, the content of the lithium salts
For 1-20 parts by weight, preferably 5-15 parts by weight；The content of the conductive agent is 5-20 parts by weight, preferably 6-15 parts by weight；
The content of the binder is 1-20 parts by weight, preferably 2-15 parts by weight；
Preferably, the electrode material layer is negative electrode material layer, and the electrode active material is negative electrode active material, the cathode
Material layer also contains lithium salts, binder and thickener；Relative to the negative electrode active material of 100 parts by weight, the content of the lithium salts
For 1-20 parts by weight, preferably 1-5 parts by weight；The content of the binder is 1-20 parts by weight, preferably 1-5 parts by weight；Institute
The content for stating thickener is 1-20 parts by weight, preferably 1-5 parts by weight；
Preferably, the electrode material layer with a thickness of 10-100 μm；
Preferably, the lithium salts is LiClO4、LiPF6、LiBF4、LiBOB、LiN(SO2CF3)2、LiCF3SO3And LiN
(SO2CF2CF3)2One of or it is a variety of.
5. a kind of preparation method of battery electrode, which is characterized in that this method comprises:
(1) electrode slurry containing electrode active material, cross-linkable copolymers, crosslinking agent and photoinitiator is provided；
(2) electrode slurry of step (1) is coated on electrode current collecting body, and dry, then under ultraviolet light, is handed over
Connection solidification is in forming electrode material layer on electrode current collecting body；
Wherein, the cross-linkable copolymers contain structural unit shown in structural unit shown in formula (1), formula (2) and formula (3) institute
The structural unit shown；
Formula (1):Formula (2):Formula (3):
Wherein, R is the alkyl of H or C1-C4, and L is the alkylidene or-R of C0-C41-O-R2, R1For the alkylidene of C0-C4, R2For
The alkylidene of C0-C4；
The crosslinking agent is one of acrylic ester cross-linking agent containing at least two esters of acrylic acid groups or a variety of, institute
Stating esters of acrylic acid group is group shown in formula (4) :-O-C (O)-C (R ')=CH2, R ' is the alkyl of H or C1-C4.
6. according to the method described in claim 5, wherein, R H, methyl or ethyl, L are the alkylidene ,-CH of C02-、-
CH2CH2-、-CH2CH2CH2-、-O-、-O-CH2-、-O-CH2CH2-、-CH2-O-、-CH2-O-CH2-、-CH2-O-CH2CH2-、-
CH2CH2-O-、-CH2CH2-O-CH2Or-CH2CH2-O-CH2CH2-；R ' is H, methyl or ethyl；
Preferably, in the cross-linkable copolymers, structural unit shown in formula (1), structural unit and formula (3) shown in formula (2)
Shown in structural unit molar ratio be 100:0.5-25:0.5-20, preferably 100:1-21:0.5-15, more preferably 100:
1-15:1-10 is still more preferably 100:1-8:1-6；
Preferably, the weight average molecular weight of the cross-linkable copolymers is 5,000-5,000,000g/mol, preferably 50,000-1,
000,000g/mol, more preferably 50,000-500,000g/mol are still more preferably 50,000-95,000g/mol.
7. method according to claim 5 or 6, wherein the crosslinking agent is ethylene glycol dimethacrylate, two propylene
Sour glycol ester, dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate,
Triethylene glycol diacrylate, tetraethylene glycol dimethylacrylate, tetraethylene glycol diacrylate, dimethacrylate -1,
3-propanediol ester, dimethacrylate -1,2- propylene glycol ester, diacrylate -1,3- propylene glycol ester, diacrylate -1,2- the third two
Alcohol ester, dimethacrylate -1,4- butanediol ester, dimethacrylate -1,3 butylene glycol ester, diacrylate -1,4- butanediol
Ester, diacrylate -1,3 butylene glycol ester, pentaerythritol diacrylate, pentaerythritol triacrylate and pentaerythrite 4 third
One of olefin(e) acid ester is a variety of, more preferably triethylene glycol dimethacrylate, triethylene glycol diacrylate, Ji Wusi
One of alcohol triacrylate and pentaerythritol tetraacrylate are a variety of；
Preferably, on the basis of the total weight of the cross-linkable copolymers and crosslinking agent, the dosage of the cross-linkable copolymers is
60-95 weight %, preferably 70-92 weight %, more preferably 70-90 weight %；The dosage of the crosslinking agent is 5-40 weight
Measure %, preferably 8-30 weight %.
8. the method according to any one of claim 5-7, wherein relative to the electrode active material of 100 parts by weight,
Total dosage of the cross-linkable copolymers and crosslinking agent is 5-100 parts by weight, preferably 10-80 parts by weight, more preferably 20-50
Parts by weight；
Preferably, the electrode material layer is positive electrode material layer, and the electrode active material is positive electrode active materials, the electrode
Slurry, which also introduces, lithium salts, conductive agent and binder；Relative to the electrode active material of 100 parts by weight, the content of the lithium salts
For 1-20 parts by weight, preferably 5-15 parts by weight；The content of the conductive agent is 5-20 amount part, preferably 6-15 parts by weight；Institute
The content for stating binder is 1-20 parts by weight, preferably 2-15 parts by weight；
Preferably, the electrode material layer is negative electrode material layer, and the electrode active material is negative electrode active material, the electrode
Slurry, which also introduces, lithium salts, binder and thickener；Relative to the negative electrode active material of 100 parts by weight, the content of the lithium salts
For 1-20 parts by weight, preferably 1-5 parts by weight；The content of the binder is 1-20 parts by weight, preferably 1-5 parts by weight；Institute
The content for stating thickener is 1-20 parts by weight, preferably 1-5 parts by weight；
Preferably, the photoinitiator be 2- hydroxy-2-methyl propiophenone, (2,4,6- trimethylbenzoyl) phosphinic acid ethyl ester,
4- dimethylaminobenzoic acid ethyl ester, 1- hydroxycyclohexyl phenyl ketone, benzoin dimethylether, methyl o-benzoylbenzoate and 4-
One of chlorobenzophenone is a variety of；
Preferably, on the basis of the total weight of the cross-linkable copolymers and crosslinking agent, the dosage of the photoinitiator is 2-15
Weight %, preferably 3-8 weight %；
Preferably, the lithium salts is LiClO4、LiPF6、LiBF4、LiBOB、LiN(SO2CF3)2、LiCF3SO3And LiN
(SO2CF2CF3)2One of or it is a variety of.
9. the method according to any one of claim 5-8, wherein the electrode material layer with a thickness of 10-100 μ
m。
10. battery electrode made from the method as described in any one of claim 5-9.
11. a kind of all-solid-state battery, wherein the all-solid-state battery includes: anode, electrolyte layer and cathode, the anode and/or
Cathode is battery electrode described in any one of claim 1-4 and 10.
12. all-solid-state battery according to claim 11, wherein the electrolyte layer is to be attached to anode and/or cathode
On polymer dielectric film, the polymer dielectric film contains polymeric matrix and the lithium that is scattered in the polymeric matrix
Salt, the polymeric matrix are polymeric matrix defined in claim 1-4.
13. all-solid-state battery according to claim 11, wherein the electrolyte layer is to be attached to anode and/or cathode
On polymer dielectric film, the preparation method of the polymer dielectric film includes:
(a) electrolyte slurry containing lithium salts, cross-linkable copolymers, crosslinking agent and photoinitiator is provided；
(b) electrolyte slurry is coated on the anode and/or cathode, and dry, then under ultraviolet light, into
Row crosslinking curing in anode and/or cathode on form electrolyte layer；
Wherein, the cross-linkable copolymers, crosslinking agent and photoinitiator are as defined in claim 5-8.
14. all-solid-state battery described in any one of 1-13 according to claim 1, wherein the electrolyte layer with a thickness of
10-200μm。
15. all-solid-state battery described in any one of 1-14 according to claim 1, wherein the cathode is attached with for surface
The negative current collector of lithium metal.
Priority Applications (1)
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| CN109206564A (en) * | 2017-07-03 | 2019-01-15 | 深圳市比亚迪锂电池有限公司 | Cross-linked polymer and polymer dielectric and preparation method thereof and high-energy-density power battery |
| CN112952100A (en) * | 2021-05-13 | 2021-06-11 | 蜂巢能源科技有限公司 | Cobalt-free anode material slurry and preparation method and application thereof |
| CN113036215A (en) * | 2019-12-24 | 2021-06-25 | 广州汽车集团股份有限公司 | Electrolyte slurry, composite positive pole piece, preparation method, lithium ion cell, lithium ion battery pack and application |
| CN113488627A (en) * | 2021-07-12 | 2021-10-08 | 江西瑞马新能源材料技术有限公司 | Solid-state silicon lithium battery anode material and preparation method thereof |
| CN113764668A (en) * | 2021-08-17 | 2021-12-07 | 广州市乐基智能科技有限公司 | Composite binder for solid lithium battery and preparation method and application method thereof |
| WO2022001429A1 (en) * | 2020-06-29 | 2022-01-06 | 珠海冠宇电池股份有限公司 | Positive electrode plate and secondary battery comprising same |
| CN117423805A (en) * | 2023-12-18 | 2024-01-19 | 北京理工大学深圳汽车研究院(电动车辆国家工程实验室深圳研究院) | Solid quasi-dry gel electrode and preparation method thereof |
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| CN109206564A (en) * | 2017-07-03 | 2019-01-15 | 深圳市比亚迪锂电池有限公司 | Cross-linked polymer and polymer dielectric and preparation method thereof and high-energy-density power battery |
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| CN112952100B (en) * | 2021-05-13 | 2021-07-30 | 蜂巢能源科技有限公司 | Cobalt-free anode material slurry and preparation method and application thereof |
| CN113488627A (en) * | 2021-07-12 | 2021-10-08 | 江西瑞马新能源材料技术有限公司 | Solid-state silicon lithium battery anode material and preparation method thereof |
| CN113488627B (en) * | 2021-07-12 | 2022-09-16 | 江西瑞马新能源材料技术有限公司 | Solid-state silicon lithium battery anode material and preparation method thereof |
| CN113764668A (en) * | 2021-08-17 | 2021-12-07 | 广州市乐基智能科技有限公司 | Composite binder for solid lithium battery and preparation method and application method thereof |
| CN117423805A (en) * | 2023-12-18 | 2024-01-19 | 北京理工大学深圳汽车研究院(电动车辆国家工程实验室深圳研究院) | Solid quasi-dry gel electrode and preparation method thereof |
| CN117423805B (en) * | 2023-12-18 | 2024-03-29 | 北京理工大学深圳汽车研究院(电动车辆国家工程实验室深圳研究院) | Solid quasi-dry gel electrode and preparation method thereof |
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