CN108695558A - A kind of all-solid-state battery core and the high-performance solid state battery comprising the battery - Google Patents
A kind of all-solid-state battery core and the high-performance solid state battery comprising the battery Download PDFInfo
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- CN108695558A CN108695558A CN201810495322.6A CN201810495322A CN108695558A CN 108695558 A CN108695558 A CN 108695558A CN 201810495322 A CN201810495322 A CN 201810495322A CN 108695558 A CN108695558 A CN 108695558A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention relates to all-solid-state battery technical fields, disclose a kind of all-solid-state battery core and the high-performance all-solid-state battery it includes the battery, wherein, positive electrode, electrolyte, negative material and the collector of all-solid-state battery core are integrated polarizing electrode, to eliminate the interface problem between four, the generation of interface impedance is avoided.And the all-solid-state battery made of the all-solid-state battery core, it may have long service life and higher electrical property, thus large-scale promotion is suitble to use.
Description
Technical field
The present invention relates to all-solid-state battery technical field, more particularly to a kind of all-solid-state battery core and include the battery
High-performance solid state battery.
Background technology
Lithium battery and sode cell are with its high-energy density, high working voltage, long circulation life, low self-discharge rate, memoryless
Effect, can fast charging and discharging and advantages of environment protection be widely used, also solve conventional liquid secondary cell
In contain a large amount of organic electrolytes, have the shortcomings that volatile, inflammable, explosive, reduce probability existing for major safety risks.
Thus, there is higher safety and machinery compared to conventional liquid battery using the all-solid-state battery of solid electrolyte
Intensity, it is also possible to realize the preparation of high capacity cell.However, in the battery core structure of all-solid-state battery, solid electrolyte
It is different from the solid-liquid contact of conventional liquid battery between solid state electrode, and it belongs to solid-solid contact.Thus, it is all solid state
Battery in charge and discharge, positive and negative anodes can continue occur volume expansion/contraction, if contact defective tightness, electrode/electrolyte it
Between just there will be huge interface impedance, or even generate crack, greatly influence battery performance.It is good complete in order to obtain
Solid state battery, common mode of operation are to use fixture to apply certain pressure in the longitudinal direction in all-solid-state battery core, therefore also
Accessory is increased, to reduce the volume and mass-energy density metric density of all-solid-state battery, limits the reality of all-solid-state battery
It applies on border.
In order to reduce the interface impedance between primary battery electrode/electrolyte, many enterprises also proposed phase on the market
The solution of pass, such as be dry application No. is a kind of battery is disclosed in 201410788427.2 Chinese patent
In dry environment, from bottom to top by negative current collector, negative material, solid electrolyte, anode composite, plus plate current-collecting body in battery pressure
It is suppressed in molding jig integral.
But negative current collector, negative material, solid electrolyte, anode composite in such battery core structure and just
Interface between the collector of pole is still more obvious.Also, they are also contacted simply by simple physical action
Together, thus over time, mutual active force will significantly weaken.Especially battery is in charge and discharge
Convergent-divergent process after, the interface between each layer can become promising apparent.Thus, also larger space is waited in improvement.
Invention content
The purpose of the present invention is to provide a kind of all-solid-state battery cores, are substantially eliminated by way of integrally polymerizeing
Caused interfacial separation in charge and discharge process and the big technical problem of the impedance that generates, and the peace of obtained all-solid-state battery
Full property and cycle life have also obtained huge promotion.
The present invention above-mentioned purpose technical scheme is that:A kind of all-solid-state battery core, including one
Plus plate current-collecting body, integrated electrode and the negative current collector that body is polymerized, wherein integrated electrode be located at plus plate current-collecting body and
Between negative current collector.
By using above-mentioned technical proposal, due to positive electrode, negative material and the electrolyte in integrated electrode herein
Integration is formd by way of polymerization, to which the interface between positive electrode, electrolyte and negative material substantially eliminates
, the presence of interface impedance is also avoided in this way.Moreover, between plus plate current-collecting body and negative current collector and integrated electrode
It is to be linked together by way of polymerization, in this way for the bonding of physics mode, mutual firmness
It can bigger.To which in the case where not using fixture, battery can also ensure higher during long-term fully electricity
Integrality thereby reduces battery and the probability of interface impedance occurs, improves the service life of battery long-time service.
Preferably, integrated electrode includes positive electrode, negative material and electrolyte, as mass fraction, wherein anode
Material include 1~5 part of polymer monomer, 0.001~0.01 part of initiator, 0.2~3 part of alkali metal salt, positive electrode active materials 6~
10 parts and 1~2 part of carbon black;Negative material includes 1~5 part of polymer monomer, 0.001~0.01 part of initiator, alkali metal salt 0.2
1~2 part of~3 parts, 6~10 parts of negative electrode active material and carbon black;Electrolyte includes 1~5 part of polymer monomer, initiator 0.001
0.2~3 part and 0.01~1 part~0.01 part, alkali metal salt filler.
Preferably, it is ethylene oxide, methyl methacrylate, acrylonitrile that the polymer monomer, which can be polymer monomer,
In any one or a few mixture.
By using above-mentioned technical proposal, the polyethylene oxide that ethylene oxide is polymerized alone, inside there are C-
O-C keys usually have compliance, are conducive to electrode/electrolyte and play the role of buffering, while its during expansion is flexible
Associated matter can be formed with electron acceptor or part inorganic electrolyte, to also ensure that the electrolyte after polymerization can be for a long time
Keep integrality.
And what methyl methacrylate polymerization obtained is polymethyl methacrylate, with larger mechanical strength, energy
It is enough effectively reduced electrolyte and occurs the probability of slight crack during convergent-divergent.
Furthermore during acrylonitrile aggregates into polyacrylonitrile in situ, alkali metal salt, positive active material and negative electrode active
Material can be distributed in the molecule of polyacrylonitrile well, and the space structure of polyacrylonitrile is netted, without electric current
In the case of generation, internal positive active material and negative electrode active material are not easy to contact and react, to not
In the case of use, battery can keep permanent electric energy.And itself has preferable heat resistance again, to battery
In charge and discharge, polyacrylonitrile is not easy to be destroyed, and then is conducive to improve the service life of battery.
Moreover, acrylonitrile can form the third acetonitrile-methylmethacrylate copolymer with methyl methacrylate again, with third
Alkene eyeball content increases, and the impact strength of polymer significantly improves, and tensile strength also improves.Meanwhile the polarity of cyano
It is very strong, to increase intermolecular active force, form hydrogen bond crosslinks structure;In turn, integrated electrode can be made to protect for a long time
Integrality is held, and makes integrated electrode during charge and discharge, can be effectively prevented from because caused by convergent-divergent
The appearance of slight crack.
Meanwhile the monomeric small molecule not exclusively polymerizeing plays the plasticization to polymer solid electrolyte, it can be further
Solid electrolyte ionic conductivity and toughness are improved, the flexibility of all solid state battery core is improved.
Preferably, the initiator can be three boron nitride ethamine, in dibenzoyl peroxide and azodiisobutyronitrile
Any one or a few mixture.
By using above-mentioned technical proposal, the stabilization that initiator compares under normal temperature state, while it can not only promote
Polymer monomer carries out polymerisation, and it can also serve as the decentralized medium of electrode material, to advantageously ensure that polymerization
The homogeneity of product.
Preferably, the alkali metal can be any one in lithium salts and sodium salt, and the sodium salt can be NaN
(SO2CF3)2,NaClO4,NaSO2CF3With NaB (C2O4)2In any one or a few mixture, the lithium salts can be LiN
(SO2CF3)2,LiClO4,LiSO2CF3With LiB (C2O4)2In any one or a few mixture.
Preferably, the filler is SiO2,BaTiO3,ZrO2,Li2Any one or a few mixture in O and EC.
Preferably, the positive electrode active materials can be any one in LFP, NCM, NCA and rich lithium, and the cathode is lived
Property material can be graphite, any one in silicon and Si-C composite material.
Preferably, the positive electrode active materials can be NaxMO2With NaxM (CN)6Any one of, and M can be
Any one in Ni, Mn, Fe, Co and Cu, the negative electrode active material are hard carbon.
Preferably, the thickness of positive electrode is 10~100 μm, and the thickness of electrolyte is 10~100 μm, the thickness of negative material
Degree is 10~100 μm.
A kind of high-performance all-solid-state battery, including above-mentioned all-solid-state battery core.
In conclusion the invention has the advantages that:
1, it is integrally polymerized between positive electrode, negative material, electrolyte and collector, to also eliminate the need for
Interface between four, and then avoid the generation of interface impedance;
2, initiator is more stable under normal temperature state, and polymer monomer can not only be promoted to carry out polymerisation.Moreover, also
The decentralized medium for potentially acting as electrode material, to advantageously ensure that the homogeneity of polymerizate;
3, positive electrode, negative material and electrolyte need not individually take cooling of making a return journey off and dry after coating, thus
The thickness that positive electrode, negative material and electrolyte can coat can reach 10 μm without rupturing, and ensure electricity in this way
In the case of the core quality of pond, the internal resistance value of battery is also reduced;
4, electrode material improves adhesiveness of the electrode material to collector in the in-situ polymerization of collection liquid surface.
Description of the drawings
Fig. 1 is the structural schematic diagram of battery;
Fig. 2 is the preparation flow figure of battery;
Fig. 3 is the structural schematic diagram of the all-solid-state battery of the core containing Stackable batteries;
Fig. 4 is the structural schematic diagram of the all-solid-state battery of the core containing coiled battery.
In figure, 1, core;11, plus plate current-collecting body;12, integrated electrode;13, negative current collector;2, aluminum plastic film;3a, just
Extreme one;3b, negative pole end one;4, shell;5a, positive terminal two;5b, negative pole end two.
Specific implementation mode
Below in conjunction with attached drawing 1, invention is further described in detail.
A kind of all-solid-state battery core, as shown in Fig. 1, core 1 include mainly plus plate current-collecting body 11, negative current collector 13
With integrated electrode 12, wherein integrated electrode 12 is between plus plate current-collecting body 11 and negative current collector 13, and three is one
What body was polymerized.Meanwhile the thickness of the positive electrode and negative material in integrated electrode 12 is 10~100 μm, electrolysis
The thickness of matter is also about 10~100 μm, and the overall thickness of positive electrode and electrolyte is 20~150 μm.
Moreover, being directed to the measurement for having done internal resistance value to the thickness of integrated electrode, and obtain as shown in following table one:
Relationship between the thickness and battery internal resistance value of one integrated electrode of table
From upper table one, it is apparent that when the integral thickness of integrated electrode 12 is less than or equal to 30 μm, battery
The trend that internal resistance value will decreased significantly pushes away the technology of all-solid-state battery to also illustrate that the thickness of battery reduces
Into there is important role.And in the case that thickness is less than 30 μm, what internal resistance declined is not very big, but whole operation requires
The comparison promoted with regard to needs is more.
Thus, from the point of view of composite factor, the preferred thickness of integrated electrode 12 of the invention is 30 μm.
Embodiment one to embodiment eight is described in further detail below in conjunction with attached drawing 2.
Embodiment one:
The preparation method of all-solid-state battery core, mainly includes the following steps that:According to the mass fraction,
Step 1:By 3 parts of ethylene oxide, 0.005 part of three boron nitride ethamine, 1.1 parts of LiN (SO2CF3)2, 8 parts of LFP, 1.5 parts of charcoals
It is black to be mixed, it stirs evenly and obtains precursor solution A;
Step 2:By 3 parts of ethylene oxide, 0.005 part of three boron nitride ethamine, 1.1 parts of LiN (SO2CF3)2, 0.5 part of SiO2Stirring is equal
Even acquisition polymer dielectric precursor solution B;
Step 3:By 3 parts of ethylene oxide, 0.005 part of three boron nitride ethamine, 1.1 parts of LiN (SO2CF3)2, 8 parts of graphite, 1.5 parts of charcoals
It is black to be mixed, it stirs evenly and obtains precursor solution C;
Step 4:Two groups of gaps between scraper and plus plate current-collecting body are adjusted separately, it is respectively that precursor solution A and presoma is molten
Liquid B is successively coated on plus plate current-collecting body, and the thickness coated is respectively 55 μm and 55 μm, and is formed precursor solution A and existed
Forerunner's laminated film one bottom, precursor solution B uniform in upper organic and inorganic distributed mutually;
Step 5:The gap between third group scraper and negative current collector is adjusted, precursor solution C is coated to negative current collector
On obtain forerunner's laminated film two, and the coating thickness of precursor solution C is 55 μm;
Step 6:Forerunner's laminated film one is combined as forerunner's laminated film three with forerunner's laminated film two by roll-in, and wherein
Precursor solution B and precursor solution C are in contact;
Step 7:Forerunner's laminated film three is heating and curing by 80 DEG C and is handled for 24 hours, membrane electrode, rolled or stacking are obtained
The all-solid-state battery battery core of in-situ polymerization is obtained afterwards.
Herein, plus plate current-collecting body is aluminium foil, and negative current collector is copper foil.Also, whole preparation process is all in dry gas
It is carried out under the protection of body.
In addition, the differing only in as shown in following table two to embodiment eight and embodiment one of embodiment two,
Embodiment two:
The preparation method of all-solid-state battery core, mainly includes the following steps that:According to the mass fraction,
Step 1:By 5 parts of methyl methacrylates, 0.01 part of dibenzoyl peroxide, 3 parts of LiClO4, 10 parts of NCM, 2 parts of carbon blacks
It is mixed, stirs evenly and obtain precursor solution A;
Step 2:By 5 parts of methyl methacrylates, 0.01 part of dibenzoyl peroxide, 3 parts of LiClO4, 1 part of EC stirs evenly and obtains
Obtain polymer dielectric precursor solution B;
Step 3:By 5 parts of methyl methacrylates, 0.01 part of dibenzoyl peroxide, 3 parts of LiClO4, 10 parts of silicon materials, 2 parts
Carbon black is mixed, and is stirred evenly and is obtained precursor solution C;
Step 4:Two groups of gaps between scraper and plus plate current-collecting body are adjusted separately, it is respectively that precursor solution A and presoma is molten
Liquid B is successively coated on plus plate current-collecting body, and the thickness coated is respectively 100 μm and 100 μm, and forms precursor solution A
In forerunner's laminated film one that bottom, precursor solution B are uniform in upper organic and inorganic distributed mutually;
Step 5:The gap between third group scraper and negative current collector is adjusted, precursor solution C is coated to negative current collector
On obtain forerunner's laminated film two, and the coating thickness of precursor solution is 100 μm;
Step 6:Forerunner's laminated film one and forerunner's laminated film two are combined as forerunner's laminated film three, and its by roll-in
Middle precursor solution B and precursor solution C are in contact;
Step 7:Forerunner's laminated film three is passed through into 100 DEG C of 36h processing that are heating and curing, obtains membrane electrode, rolled or stacking
The all-solid-state battery battery core of in-situ polymerization is obtained afterwards.
Herein, plus plate current-collecting body is aluminium net, and negative current collector is copper mesh.Also, whole preparation process is all in dry gas
It is carried out under the protection of body.
Embodiment three:
A kind of preparation method of all-solid-state battery core, mainly includes the following steps that:According to the mass fraction,
Step 1:By 1 part of acrylonitrile, 0.001 part of azodiisobutyronitrile, 0.2 part of LiSO2CF3, 6 parts of NCA, 1 part of carbon black mixed
It closes, stirs evenly and obtain precursor solution A;
Step 2:By 1 part of acrylonitrile, 0.001 part of azodiisobutyronitrile, 0.2 part of LiSO2CF3, 1 part of BaTiO3Stir evenly acquisition
Polymer dielectric precursor solution B;
Step 3:By 1 part of acrylonitrile, 0.001 part of azodiisobutyronitrile, 0.2 part of LiSO2CF3, 6 parts of Si-C composite materials, 1 part
Carbon black is mixed, and is stirred evenly and is obtained precursor solution C;
Step 4:Two groups of gaps between scraper and plus plate current-collecting body are adjusted separately, by precursor solution A and precursor solution B
Successively be coated on plus plate current-collecting body, and the thickness coated is respectively 10 μm and 10 μm, and formed precursor solution A bottom,
Forerunner's laminated film one uniform in upper organic and inorganic distributed mutually precursor solution B;
Step 5:The gap between third group scraper and negative current collector is adjusted, precursor solution C is coated to negative current collector
On obtain forerunner's laminated film two, and the coating thickness of precursor solution C is 10 μm;
Step 6:Forerunner's laminated film one and forerunner's laminated film two are combined as forerunner's laminated film three, and its by roll-in
Middle precursor solution B and precursor solution C are in contact;
Step 7:Forerunner's laminated film three is passed through into 60 DEG C of 8h processing that are heating and curing, membrane electrode is obtained, after rolled or stacking
Obtain the all-solid-state battery battery core of in-situ polymerization;
Herein, plus plate current-collecting body is carbon cloth, and negative current collector is carbon cloth.Also, whole preparation process is all in dry gas
The lower progress of protection.
Example IV:
A kind of preparation method of all-solid-state battery core, mainly includes the following steps that:According to the mass fraction,
Step 1:By 1 part of ethylene oxide, 1 part of methyl methacrylate, 0.001 part of three boron nitride ethamine, 0.45 part of LiB
(C2O4)2, 0.2 part of LiClO4, 8 parts of rich lithiums, 1 part of carbon black mixed, stirs evenly and obtain precursor solution A;
Step 2:By 1 part of ethylene oxide, 1 part of methyl methacrylate, 0.001 part of three boron nitride ethamine, 0.45 part of LiB
(C2O4)2, 0.2 part of LiClO4, 0.01 part of Li2O, which is stirred evenly, obtains polymer dielectric precursor solution B;
Step 3:By 1 part of ethylene oxide, 1 part of methyl methacrylate, 0.001 part of three boron nitride ethamine, 0.45 part of LiB
(C2O4)2, 6 parts of silicon materials, 2 parts of carbon blacks are mixed, and are stirred evenly and are obtained precursor solution C;
Step 4:The gap between plus plate current-collecting body between two groups of scrapers is adjusted separately, respectively by precursor solution A and presoma
Solution B is successively coated on plus plate current-collecting body, and the thickness coated is respectively 60 μm and 80 μm, and forms precursor solution A
In forerunner's laminated film one that bottom, precursor solution B are uniform in upper organic and inorganic distributed mutually;
Step 5:The thickness between third group scraper gap thickness and negative current collector is adjusted, precursor solution C is coated to negative
Forerunner's laminated film two is obtained on the collector of pole, and the coating thickness of precursor solution C is 10 μm;
Step 6:Forerunner's laminated film one and forerunner's laminated film two are combined as forerunner's laminated film three, and its by roll-in
Middle precursor solution B and precursor solution C are in contact;
Step 7:Film 3 is passed through into 100 DEG C of 36h processing that are heating and curing, membrane electrode is obtained, original is obtained after rolled or stacking
The all-solid-state battery battery core of position polymerization;
Herein, plus plate current-collecting body is stainless steel foil, and negative current collector is nickel foil.Also, whole preparation process is all in dry gas
It is carried out under the protection of body.
Embodiment five:
A kind of preparation method of all-solid-state battery core, mainly includes the following steps that:According to the mass fraction,
Step 1:By 2 parts of ethylene oxide, 2 parts of acrylonitrile, 0.005 part of dibenzoyl peroxide, 0.005 part of azodiisobutyronitrile,
3 parts of NaN (SO2CF3)2, 8 parts of NaxMnO2, 1 part of carbon black mixed, and is stirred evenly and is obtained precursor solution A;
Step 2:By 2 parts of ethylene oxide, 2 parts of acrylonitrile, 0.005 part of dibenzoyl peroxide, 0.005 part of azodiisobutyronitrile,
1.1 parts of NaN (SO2CF3)2, 0.5 part of SiO2, 0.01 part of ZrO2, stir evenly and obtain polymer dielectric precursor solution B;Step
Three:By 2 parts of ethylene oxide, 2 parts of acrylonitrile, 0.005 part of dibenzoyl peroxide, 0.005 part of azodiisobutyronitrile, 0.2 part of NaN
(SO2CF3)2, 8 parts of hard carbons, 1.5 parts of carbon blacks are mixed, and are stirred evenly and are obtained precursor solution C;
Step 4:Two groups of gaps between scraper and plus plate current-collecting body are adjusted separately, it is respectively that precursor solution A and presoma is molten
Liquid B is successively coated on plus plate current-collecting body, and the thickness coated is respectively 55 μm and 10 μm, and is formed precursor solution A and existed
Forerunner's laminated film one bottom, precursor solution B uniform in upper organic and inorganic distributed mutually;
Step 5:The gap between third group scraper and negative current collector is adjusted, precursor solution C is coated to negative current collector
On obtain forerunner's laminated film two, and the thickness of precursor solution C coatings is 100 μm;
Step 6:Forerunner's laminated film one is combined as forerunner's laminated film three with forerunner's laminated film two by roll-in, and wherein
Precursor solution B and precursor solution C are in contact;
Step 7:Forerunner's laminated film three is heating and curing by 80 DEG C and is handled for 24 hours, membrane electrode, rolled or stacking are obtained
The all-solid-state battery battery core of in-situ polymerization is obtained afterwards.
Herein, plus plate current-collecting body is stainless (steel) wire, and negative current collector is nickel screen.Also, whole preparation process is all dry
It is carried out under the protection of pathogenic dryness body.
Embodiment six:
A kind of preparation method of all-solid-state battery core, mainly includes the following steps that:According to the mass fraction,
Step 1:By 3 parts of methyl methacrylates, 2 parts of acrylonitrile, 0.005 part is crossed azodiisobutyronitrile, 3 parts of NaClO4, 10 parts
NaxFe(CN)6, 2 parts of carbon blacks are mixed, and are stirred evenly and are obtained precursor solution A;
Step 2:By 3 parts of methyl methacrylates, 2 parts of acrylonitrile, 0.01 part is crossed azodiisobutyronitrile, 3 parts of NaClO4, 1 part of EC
It stirs evenly and obtains polymer dielectric precursor solution B;
Step 3:By 3 parts of methyl methacrylates, 2 parts of acrylonitrile, 0.001 part is crossed azodiisobutyronitrile, 3 parts of NaClO4, 10 parts
Silicon materials, 2 parts of carbon blacks are mixed, and are stirred evenly and are obtained precursor solution C;
Step 4:Two groups of gaps between scraper and plus plate current-collecting body are adjusted separately, it is respectively that precursor solution A and presoma is molten
Liquid B is successively coated on plus plate current-collecting body, and the thickness coated is respectively 10 μm and 55 μm, and is formed precursor solution A and existed
Forerunner's laminated film one bottom, precursor solution B uniform in upper and organic and inorganic distributed mutually;
Step 5:The gap between third group scraper and negative current collector is adjusted, precursor solution C is coated to negative current collector
On obtain forerunner's laminated film two, and the thickness of precursor solution C coatings is 20 μm;
Step 6:Forerunner's laminated film one and forerunner's laminated film two are combined as forerunner's laminated film three, and its by roll-in
Middle precursor solution B and precursor solution C are in contact;
Step 7:Forerunner's laminated film three is heating and curing by 100 DEG C and is handled for 24 hours, membrane electrode, rolled or stacking are obtained
The all-solid-state battery battery core of in-situ polymerization is obtained afterwards.
Herein, plus plate current-collecting body is aluminium net, and negative current collector is copper mesh.Also, whole preparation process is all in dry gas
It is carried out under the protection of body.
Embodiment seven:
A kind of preparation method of all-solid-state battery core, mainly includes the following steps that:According to the mass fraction,
Step 1:By 1 part of acrylonitrile, 1 part of ethylene oxide, 1 part of methyl methacrylate, 0.001 part of three boron nitride ethamine,
0.001 part of dibenzoyl peroxide, 0.2 part of NaSO2CF3, 6 parts of NaxCoO2, 1 part of carbon black is mixed, before stirring evenly acquisition
Drive liquid solution A;
Step 2:By 1 part of acrylonitrile, 1 part of ethylene oxide, 1 part of methyl methacrylate, 0.001 part of three boron nitride ethamine,
0.001 part of dibenzoyl peroxide, 0.2 part of NaSO2CF3, 1 part of BaTiO3It is molten to stir evenly acquisition polymer dielectric presoma
Liquid B;Step 3:By 1 part of acrylonitrile, 1 part of ethylene oxide, 1 part of methyl methacrylate, 0.001 part of three boron nitride ethamine,
0.001 part of dibenzoyl peroxide, 0.2 part of NaSO2CF3, 6 parts of Si-C composite materials, 1 part of carbon black mixed, stirs evenly and obtain
Obtain precursor solution C;
Step 4:Two groups of gaps between scraper and plus plate current-collecting body are adjusted separately, by precursor solution A and precursor solution B
It is successively coated on plus plate current-collecting body, and the thickness coated is respectively 50 μm and 100 μm, formation precursor solution A is at bottom, preceding
Drive the liquid solution B forerunner laminated films one uniform in upper organic and inorganic distributed mutually;
Step 5:The gap between third group scraper and negative current collector is adjusted, precursor solution C is coated to negative current collector
On obtain forerunner's laminated film two, the thickness of precursor solution C coatings is 20 μm;
Step 6:Forerunner's laminated film one and forerunner's laminated film two are combined as forerunner's laminated film three, and its by roll-in
Middle precursor solution B and precursor solution C are in contact;
Step 7:Forerunner's laminated film three is passed through into 60 DEG C of 36h processing that are heating and curing, obtains membrane electrode, rolled or stacking
The all-solid-state battery battery core of in-situ polymerization is obtained afterwards;
Herein, plus plate current-collecting body is carbon cloth, and negative current collector is carbon cloth.Also, whole preparation process is all in dry gas
The lower progress of protection.
Embodiment eight:
A kind of preparation method of all-solid-state battery core, mainly includes the following steps that:According to the mass fraction,
Step 1:By 1 part of ethylene oxide, 0.01 part of methyl methacrylate, 0.001 part of three boron nitride ethamine, 0.45 part of NaB
(C2O4)2, 0.2 part of NaN (SO2CF3)2, 8 parts of NaxCu(CN)6, 1 part of carbon black mixed, and is stirred evenly and is obtained precursor solution A;
Step 2:By 5 parts of ethylene oxide, 0.001 part of methyl methacrylate, 0.001 part of three boron nitride ethamine, 0.45 part of NaB
(C2O4)2, 0.2 part of NaN (SO2CF3)2, 0.01 part of ZrO2It stirs evenly and obtains polymer dielectric precursor solution B;
Step 3:By 3 parts of ethylene oxide, 0.005 part of methyl methacrylate, 0.001 part of three boron nitride ethamine, 0.45 part of NaB
(C2O4)2, 0.2 part of NaN (SO2CF3)2, 6 parts of silicon materials, 2 parts of carbon blacks are mixed, and are stirred evenly and are obtained precursor solution C;
Step 4:The gap between plus plate current-collecting body between two groups of scrapers is adjusted separately, respectively by precursor solution A and presoma
Solution B is successively coated on plus plate current-collecting body, and the thickness coated is respectively 60 μm and 80 μm, and forms precursor solution A
In forerunner's laminated film one that bottom, precursor solution B are uniform in upper and organic and inorganic distributed mutually;
Step 5:The thickness between third group scraper gap thickness and negative current collector is adjusted, precursor solution C is coated to negative
Forerunner's laminated film two is obtained on the collector of pole, and the thickness of precursor solution C coatings is 10 μm;
Step 6:Forerunner's laminated film one and forerunner's laminated film two are combined as forerunner's laminated film three, and its by roll-in
Middle precursor solution B and precursor solution C are in contact;
Step 7:Film 3 is passed through into 100 DEG C of 36h processing that are heating and curing, membrane electrode is obtained, original is obtained after rolled or stacking
The all-solid-state battery battery core of position polymerization;
Herein, plus plate current-collecting body is carbon cloth, and negative current collector is carbon cloth.Also, whole preparation process is all in dry gas
The lower progress of protection.
Comparative example one:
Step 1:Under dry gas protection, according to the mass fraction, by 8 parts of LFP, 1.1 parts of LiN (SO2CF3)2, 1.5 parts of carbon blacks
It with 3 parts of polyethylene oxide, is added in acetonitrile, stirs evenly, obtain slurry A;
Step 2:Slurry A is equably scratched on aluminium foil, after heating, drying, obtains anode layer;
Step 3:Under dry gas protection, according to the mass fraction, by 8 parts of graphite, 1.1 parts of LiN (SO2CF3)2, 1.5 parts of carbon blacks
It with 3 parts of polyethylene oxide, is added in acetonitrile, stirs evenly, obtain slurry B;
Step 4:Slurry B is equably scratched on copper foil, after drying, obtains negative electrode layer;
Step 5:Under dry gas protection, according to the mass fraction, by 3 parts of polyethylene oxide, 1.1 parts of LiN (SO2CF3)2And
0.5 part of SiO2, it is added in acetonitrile, stirs evenly acquisition solution C;
Step 6:Slurry C is cast on Teflon mould, is formed a film after heating solvent evaporated, in order to ensure to take off film
Integrality, it is 50 μm to need film thickness.
Step 7:In anode layer, it is laminated above-mentioned polymer electrolyte film, then is laminated negative electrode layer assembled battery.Test
Battery battery performance under the conditions of 60 DEG C, for the first time discharge capacity poor compared to 1 in-situ polymerization battery core of embodiment are kept with capacity
Rate.
Comparative example two:
Step 1:Under dry gas protection, according to the mass fraction, by 8 parts of rich lithiums, 0.45 part of LiB (C2O4)2, 0.2 part
LiClO4, 1 part of carbon black, 1 part of polyethylene oxide and 1 part of polymethyl methacrylate are added in acetonitrile, stir evenly, starched
Expect A;Step 2:Slurry A is equably scratched on stainless steel foil, after heating, drying, obtains anode layer;
Step 3:Under dry gas protection, according to the mass fraction, by 6 parts of silicon, 0.45 part of LiB (C2O4)2, 0.2 part of LiClO4,
2 parts of carbon blacks, 1 part of polyethylene oxide and 1 part of polymethyl methacrylate are added in acetonitrile, stir evenly, and obtain slurry B;Step
Four:Slurry B is equably scratched on nickel foil, after drying, obtains negative electrode layer;
Step 5:Under dry gas protection, according to the mass fraction, by 1 part of polyethylene oxide, 1 part of polymethyl methacrylate,
0.45 part of LiB (C2O4)2, 0.2 part of LiClO4And 0.01 part of Li2O is added in acetonitrile, stirs evenly acquisition solution C;Step
Six:Slurry C is cast on Teflon mould, is formed a film after heating solvent evaporated, in order to ensure, in the integrality for taking off film, to need
It is 50 μm to want film thickness.
Step 7:In anode layer, it is laminated above-mentioned polymer electrolyte film, then is laminated negative electrode layer assembled battery.
Comparative example three:
Step 1:Under dry gas protection, according to the mass fraction, by 8 parts of NaxCu(CN)6, 0.45 part of NaB (C2O4)2, 0.2
Part NaN (SO2CF3)2, 1 part of carbon black, 1 part of polyethylene oxide, 0.01 part of polymethyl methacrylate is added in acetonitrile, and stirring is equal
It is even, obtain slurry A;
Step 2:Slurry A is equably scratched on carbon cloth, after heating, drying, obtains anode layer;
Step 3:Under dry gas protection, according to the mass fraction, by 6 parts of hard carbons, 0.45 part of NaB (C2O4)2, 0.2 part of NaN
(SO2CF3)2, 2 parts of carbon blacks, 3 parts of polyethylene oxide and 0.005 part of polymethyl methacrylate be added in acetonitrile, stir evenly,
Obtain slurry B;
Step 4:Slurry B is equably scratched on carbon cloth, after drying, obtains negative electrode layer;
Step 5:Under dry gas protection, according to the mass fraction, by 5 parts of polyethylene oxide, 0.001 part of polymethylacrylic acid
Methyl esters, 0.45 part of NaB (C2O4)2, 0.2 part of NaN (SO2CF3)2And 0.01 part of ZrO2, it is added in acetonitrile, stirs evenly acquisition
Solution C;
Step 6:Slurry C is poured and is prolonged on Teflon mould, is formed a film after heating solvent evaporated, in order to ensure to take off film
Integrality, it is 50 μm to need film thickness.
Step 7:In anode layer, it is laminated above-mentioned polymer electrolyte film, then is laminated negative electrode layer assembled battery.
Test the performance of battery:
Testing example two is to embodiment nine and comparative example one to the all-solid-state battery capacity of comparative example three under the conditions of 60 DEG C
The variation of conservation rate and the internal resistance of cell, as shown in following table two,.
The variation of two all-solid-state battery capacity retention ratio of table and the internal resistance of cell
It is all relatively high from capacity retention ratio after 500 cycles of the all-solid-state battery core that can be seen that the present invention in upper table two,
Meanwhile embodiment two, embodiment five and embodiment nine being compared with comparative example one to comparative example three respectively, it can be seen that this
The internal resistance of the all-solid-state battery core of invention itself is just compared small, and internal resistance of cell increase is smaller after 500 cycles, to
Just illustrate that the interface impedance of battery does not obviously increase substantially.Thus, it is produced with the all-solid-state battery core of the present invention
All-solid-state battery is suitble to multi-field used.
Embodiment ten:
A kind of all-solid-state battery has mainly used the core 1 of one all-solid-state battery core of embodiment, and core 1 divides for stacking herein
It is formula and two kinds coiled.As shown in Fig. 2, include mainly packet for core 1 is stacked all-solid-state battery
The aluminum plastic film 2 being rolled in outside battery, and on aluminum plastic film 2 carry one 3b of one 3a of positive terminal and negative pole end, and one 3a of positive terminal and
One 3b of negative pole end is connected with positive electrode and negative material respectively.
As shown in Fig. 3, it for core 1 is coiled all-solid-state battery, is mainly wrapped in outside core 1
Shell 4, the end of shell 4 is with two 5b of two 5a of positive terminal and negative pole end, and two 5b points of two 5a of positive terminal and negative pole end
It is not connected with the positive electrode of core 1 and negative material.
This specific embodiment is only explanation of the invention, is not limitation of the present invention, people in the art
Member can as needed make the present embodiment the modification of not creative contribution after reading this specification, but as long as at this
It is all protected by Patent Law in the right of invention.
Claims (10)
1. a kind of all-solid-state battery core, it is characterised in that:Including plus plate current-collecting body (11), the integrated electrode being integrally polymerized
(12) and negative current collector (13), wherein integrated electrode (12) be located at plus plate current-collecting body (11) and negative current collector (13) it
Between.
2. a kind of all-solid-state battery core according to claim 1, it is characterised in that:Integrated electrode (12) includes positive material
Material, negative material and electrolyte, according to the mass fraction, wherein positive electrode includes 1~5 part of polymer monomer, initiator 0.001
1~2 part of~0.01 part, 0.2~3 part of alkali metal salt, 6~10 parts of positive electrode active materials and carbon black;Negative material includes polymer
1~5 part of monomer, 0.001~0.01 part of initiator, 0.2~3 part of alkali metal salt, 6~10 parts of negative electrode active material and carbon black 1~2
Part;Electrolyte includes 1~5 part of polymer monomer, 0.001~0.01 part of initiator, 0.2~3 part and 0.01~1 part of alkali metal salt
Filler.
3. a kind of all-solid-state battery core according to claim 2, it is characterised in that:The polymer monomer can be epoxy
Any one or a few mixture in ethane, methyl methacrylate, acrylonitrile.
4. a kind of all-solid-state battery core according to claim 2, it is characterised in that:The initiator can be three boron nitride
Ethamine, any one or a few the mixture in dibenzoyl peroxide and azodiisobutyronitrile.
5. a kind of all-solid-state battery core according to claim 2, it is characterised in that:The alkali metal can be lithium salts and sodium
Any one in salt, the sodium salt can be NaN (SO2CF3)2,NaClO4,NaSO2CF3With NaB (C2O4)2In any one
Or several mixtures, the lithium salts can be LiN (SO2CF3)2,LiClO4,LiSO2CF3With LiB (C2O4)2In it is any one
Kind or several mixtures.
6. a kind of all-solid-state battery core according to claim 2, it is characterised in that:The filler can be SiO2,
BaTiO3,ZrO2,Li2Any one or a few mixture in O and EC.
7. a kind of all-solid-state battery core according to claim 2, it is characterised in that:The positive electrode active materials can be
Any one in LFP, NCM, NCA and rich lithium, the negative electrode active material can be graphite, in silicon and Si-C composite material
Any one.
8. a kind of all-solid-state battery core according to claim 2, it is characterised in that:The positive electrode active materials can be
NaxMO2With NaxM (CN)6In any one, and M can be any one in Ni, Mn, Fe, Co and Cu, and the cathode is lived
Property material be hard carbon.
9. a kind of all-solid-state battery core according to claim 2, it is characterised in that:The thickness of positive electrode is 10~100 μ
The thickness of m, electrolyte are 10~100 μm, and the thickness of negative material is 10~100 μm.
10. a kind of high-performance all-solid-state battery, it is characterised in that:Including described in any one of claim 1 to 9 claim
A kind of all-solid-state battery core.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110336077A (en) * | 2019-07-02 | 2019-10-15 | 华南理工大学 | A kind of lithium ion battery of high voltage nickel-cobalt-manganternary ternary anode material |
| CN111969243A (en) * | 2020-08-28 | 2020-11-20 | 杭州肄康新材料有限公司 | Sodium ion solid-state battery and preparation process thereof |
| CN112542610A (en) * | 2020-11-16 | 2021-03-23 | 欣旺达电动汽车电池有限公司 | All-solid-state battery and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11171912A (en) * | 1997-12-12 | 1999-06-29 | Showa Denko Kk | Polymerizable composition and use thereof |
| WO2002078114A1 (en) * | 2001-03-27 | 2002-10-03 | Sharp Kabushiki Kaisha | Lithium polymer secondary battery and production method therefor |
| US20030180624A1 (en) * | 2002-03-22 | 2003-09-25 | Bookeun Oh | Solid polymer electrolyte and method of preparation |
| CN101106187A (en) * | 2006-07-14 | 2008-01-16 | 日产自动车株式会社 | Cell electrode |
| CN101475663A (en) * | 2009-01-21 | 2009-07-08 | 中国科学院长春应用化学研究所 | Method for preparing ion liquid type gel polymer electrolyte and battery by in situ polymerization |
| WO2010089891A1 (en) * | 2009-02-09 | 2010-08-12 | トヨタ自動車株式会社 | Method for producing solid electrolyte material-containing sheet |
| CN104681866A (en) * | 2015-02-26 | 2015-06-03 | 广东烛光新能源科技有限公司 | Lithium sulfur battery and preparation method thereof |
| CN106207086A (en) * | 2016-08-15 | 2016-12-07 | 无锡海特新材料研究院有限公司 | High power capacity solid lithium ion battery negative material and battery cathode and preparation method thereof |
| CN107742728A (en) * | 2017-10-31 | 2018-02-27 | 中国科学院宁波材料技术与工程研究所 | Electrolyte/electrode interface integrated structure technique in a kind of solid lithium battery |
-
2018
- 2018-05-22 CN CN201810495322.6A patent/CN108695558B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11171912A (en) * | 1997-12-12 | 1999-06-29 | Showa Denko Kk | Polymerizable composition and use thereof |
| WO2002078114A1 (en) * | 2001-03-27 | 2002-10-03 | Sharp Kabushiki Kaisha | Lithium polymer secondary battery and production method therefor |
| CN1528028A (en) * | 2001-03-27 | 2004-09-08 | ������������ʽ���� | Lithium polymer secondary battery and production method therefor |
| US20030180624A1 (en) * | 2002-03-22 | 2003-09-25 | Bookeun Oh | Solid polymer electrolyte and method of preparation |
| CN101106187A (en) * | 2006-07-14 | 2008-01-16 | 日产自动车株式会社 | Cell electrode |
| CN101475663A (en) * | 2009-01-21 | 2009-07-08 | 中国科学院长春应用化学研究所 | Method for preparing ion liquid type gel polymer electrolyte and battery by in situ polymerization |
| WO2010089891A1 (en) * | 2009-02-09 | 2010-08-12 | トヨタ自動車株式会社 | Method for producing solid electrolyte material-containing sheet |
| CN104681866A (en) * | 2015-02-26 | 2015-06-03 | 广东烛光新能源科技有限公司 | Lithium sulfur battery and preparation method thereof |
| CN106207086A (en) * | 2016-08-15 | 2016-12-07 | 无锡海特新材料研究院有限公司 | High power capacity solid lithium ion battery negative material and battery cathode and preparation method thereof |
| CN107742728A (en) * | 2017-10-31 | 2018-02-27 | 中国科学院宁波材料技术与工程研究所 | Electrolyte/electrode interface integrated structure technique in a kind of solid lithium battery |
Non-Patent Citations (2)
| Title |
|---|
| ZHOU,DONG等: "In situ synthesis of hierarchical poly(ionic liquid)-based solid electrolytes for high-safety lithium-ion and sodium-ion batteries", 《NANO ENERGY 》 * |
| 崔艳艳: "高性能锂电池聚合物电解质的原位制备与性能研究", 《中国优秀硕士学位论文全文数据库•工程科技Ⅰ辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110336077A (en) * | 2019-07-02 | 2019-10-15 | 华南理工大学 | A kind of lithium ion battery of high voltage nickel-cobalt-manganternary ternary anode material |
| CN111969243A (en) * | 2020-08-28 | 2020-11-20 | 杭州肄康新材料有限公司 | Sodium ion solid-state battery and preparation process thereof |
| CN112542610A (en) * | 2020-11-16 | 2021-03-23 | 欣旺达电动汽车电池有限公司 | All-solid-state battery and preparation method thereof |
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