CN105470576B - A kind of high pressure lithium battery electric core and preparation method thereof, lithium ion battery - Google Patents
A kind of high pressure lithium battery electric core and preparation method thereof, lithium ion battery Download PDFInfo
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- CN105470576B CN105470576B CN201410437044.0A CN201410437044A CN105470576B CN 105470576 B CN105470576 B CN 105470576B CN 201410437044 A CN201410437044 A CN 201410437044A CN 105470576 B CN105470576 B CN 105470576B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 26
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- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- SOYRXQWJIVCERX-UHFFFAOYSA-N carbonic acid;1,1-dichloroprop-1-ene Chemical compound OC(O)=O.CC=C(Cl)Cl SOYRXQWJIVCERX-UHFFFAOYSA-N 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- JKJJSJJGBZXUQV-UHFFFAOYSA-N methyl 2-methylidenebutanoate Chemical compound CCC(=C)C(=O)OC JKJJSJJGBZXUQV-UHFFFAOYSA-N 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229960000380 propiolactone Drugs 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
Classifications
-
- 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
-
- 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
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Electrolyte to overcome the problems, such as high pressure lithium battery in the prior art is oxidizable and lithium battery performance is caused to decline, and the present invention provides a kind of high pressure lithium battery electric cores, including anode, cathode and the electrolyte between anode and cathode；The electrolyte includes inorganic electrolyte layer and the polyelectrolyte floor positioned at the inorganic electrolyte layer surface；The inorganic electrolyte layer is located at the positive electrode surface, and the polyelectrolyte floor is located at the negative terminal surface.Meanwhile the invention also discloses the preparation method of above-mentioned high pressure lithium battery electric core and using the lithium ion battery of the high pressure lithium battery electric core.High pressure lithium battery electric core provided by the invention can overcome electrolyte oxidation and a large amount of negative issues for generating, conducive to the security performance and cycle performance for improving lithium battery.
Description
Technical field
The invention belongs to high-voltage lithium ion battery field more particularly to a kind of high pressure lithium battery electric core and preparation method thereof,
And the high-voltage lithium ion battery using the high pressure lithium battery electric core.
Background technique
Lithium ion battery is compared with other batteries, and with light weight, small in size, operating voltage is high, energy density is high, output
Power is big, charge efficiency is high, memory-less effect, the advantages that having extended cycle life, and not only obtains in fields such as mobile phone, laptops
It is widely applied, and is also considered as one of electric vehicle, the optimal selection of large-scale energy storage device.But current smart phone,
The electronic digitals such as tablet computer product is higher and higher to the energy density requirement of battery, so that commercial li-ion battery is difficult to meet
It is required that.It is the most effective approach for promoting lithium ion battery energy density using high capacity positive electrode or high-voltage anode material.
The research of high-voltage anode material focuses primarily on LiNi at present0.5Mn1.5O4、LiCoPO4、LiNiPO4Equal materials,
Its discharge platform is respectively 4.7V, 4.8V and 5.1V, and charge cutoff voltage is above 4.5V.High capacity positive electrode is with rich lithium layer
Shape solid-solution material is research hotspot, and the premise of release high capacity is that material is charged to 4.5V or more.Commercial electricity at present
The operating voltage of solution liquid is 4.3V hereinafter, using that can be oxidized such as under 4.5V or more voltage, causes side reaction to increase, battery follows
The problems such as ring performance is poor, safety declines, it is difficult to be applied in high pressure lithium battery.
Summary of the invention
The technical problem to be solved by the present invention is to the electrolyte for prior art mesohigh lithium battery is oxidizable and lead
The problem of causing the decline of lithium battery performance, provides a kind of high pressure lithium battery electric core.
It is as follows that the present invention solves technical solution used by above-mentioned technical problem:
A kind of high pressure lithium battery electric core is provided, including anode, cathode and the electrolyte between anode and cathode；Institute
Stating electrolyte includes inorganic electrolyte layer and the polyelectrolyte floor positioned at the inorganic electrolyte layer surface；The no electromechanics
Solution matter layer is located at the positive electrode surface, and the polyelectrolyte floor is located at the negative terminal surface.
The present invention by being arranged inorganic electrolyte layer and polyelectrolyte floor between a positive electrode and a negative electrode, it is ensured that anode
The normal performance of capacity under high voltages.On the one hand the ionic conductivity of positive electrode can be improved in inorganic electrolyte layer, while can
The side reaction between electrolyte and high-voltage anode material is avoided, the performance of high pressure lithium battery has been effectively ensured.However, by big
Amount experiment discovery, if inorganic electrolyte layer is directly contacted with cathode, inorganic electrolyte layer will be by the negative electrode material of low potential also
Original causes electrolyte electronic conductance to increase and cause battery short circuit.In the present invention, also have between inorganic electrolyte layer and cathode
There is polyelectrolyte floor to can avoid the problem of inorganic electrolyte layer is reduced under low potential, polyelectrolyte floor ensure that
The normal performance of low potential capacity of negative plates, the electrolyte of double-layer structure barrier layer each other, can effectively block respectively because of potential problem
Bring side reaction guarantees the high voltage and high-energy density of battery, is conducive to improve battery safety height and cycle performance.
Meanwhile the present invention also provides the preparation method of above-mentioned high pressure lithium battery electric core, including by the anode stacked gradually,
Inorganic electrolyte layer, thin polymer film, cathode compression moulding, then adsorb electrolyte in thin polymer film；Formed includes just
Pole, inorganic electrolyte layer, polyelectrolyte floor and cathode the high pressure lithium battery electric core.
In addition the present invention also provides a kind of lithium ion battery, including shell and it is located at the intracorporal battery core of the shell, it is described
Battery core is above-mentioned high pressure lithium battery electric core.
Specific embodiment
In order to which the technical problems, technical solutions and beneficial effects solved by the present invention is more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
High pressure lithium battery electric core provided by the invention includes anode, cathode and the electrolysis between anode and cathode
Matter；The electrolyte includes inorganic electrolyte layer and the polyelectrolyte floor positioned at the inorganic electrolyte layer surface；It is described
Inorganic electrolyte layer is located at the positive electrode surface, and the polyelectrolyte floor is located at the negative terminal surface.
In the present invention, the anode in high pressure lithium battery electric core is not particularly limited, existing high pressure lithium specifically can be used
The anode generallyd use in battery.Specifically, the anode includes plus plate current-collecting body and the positive material on plus plate current-collecting body
Material.
The type of the plus plate current-collecting body is known to those skilled in the art, such as can be selected from aluminium foil, copper foil, punching
Hole steel band.
Above-mentioned positive electrode includes positive active material, conductive agent and the second binder.Specifically, the positive electrode active material
Matter is selected from LiNi0.5Mn1.5O4、LiMn2O4、LiCoPO4、LiNiPO4、Li3V3(PO4)3One of or it is a variety of.
The conductive agent is not particularly limited in the present invention, can be the positive conductive agent of this field routine, such as acetylene
At least one of black, carbon nanotube, HV, carbon black.Wherein, on the basis of the weight of positive active material, the conductive agent
Content is 0.1-20wt%, preferably 1-10wt%.
The type and content of second binder are known to those skilled in the art, such as fluorine resin and polyolefin
One or more of compound such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE) (PTFE) and butadiene-styrene rubber (SBR).Generally
For, according to the difference of adhesive therefor type, on the basis of the weight of positive active material, the content of the second binder is
0.01-10wt%, preferably 0.02-5wt%.
It further include solid electrolyte additive, the solid state electrolysis in the positive electrode under preferable case in the present invention
Matter additive is selected from LiNbO3、LiTaO3、Lix1La1/(3-x1)TaO3、Li3PO4、Lix2Tiy2(PO4)3、Lix3Aly3Tiz3(PO4)3、
Li2SiO3、Li2O、Li2S、Li2S-P2S5、Li2S-SiS2-P2S5、Lix4Siy4Sz4、Lix5Py5Sz5、LiBO2、Li3.6Si0.6P0.4O4
One of or it is a variety of, wherein 0 < x1< 3；0 < x22,0 < y of <2< 3；0 < x32,0 < y of <31,0 < z of <3< 3；0 < x4
3,0 < y of <42,0 < z of <4< 4；0 < x53,0 < y of <53,0 < z of <5< 7.
When also containing above-mentioned solid electrolyte additive in positive electrode, the high pressure lithium battery electric core is filled in high magnification
There is more preferably cycle performance under discharging condition.
The content of above-mentioned solid electrolyte additive can change in a big way, and those skilled in the art can be according to reality
Situation is adjusted, and under preferable case, on the basis of the weight of positive active material, the content of solid electrolyte additive is
0.1-50wt%, preferably 0.5-20wt%.
According to the present invention, the cathode in above-mentioned high pressure lithium battery electric core is not particularly limited, and existing high pressure specifically can be used
The cathode generallyd use in lithium battery.Specifically, the cathode includes negative current collector and on the negative current collector
Negative electrode material.
The various negative current collectors that the negative current collector is known to the skilled person, for example, can selected from aluminium foil,
One or more of copper foil, nickel plated steel strip, Punching steel strip.
The negative electrode material includes negative electrode active material and third binder.
The negative electrode active material is not particularly limited, and the cathode that is embeddable and releasing lithium of this field routine can be used
Active material.Specifically, the negative electrode active material is selected from one of carbon material, tin alloy, silicon alloy, silicon, tin, germanium or more
Kind.For above-mentioned carbon material, specifically can be selected from natural graphite, natural modified graphite, artificial graphite, petroleum coke, organic cracking carbon,
One of carbonaceous mesophase spherules, carbon fiber, tin alloy and silicon alloy are a variety of, preferably artificial graphite and natural modified graphite.
In general, according to the actual situation, cathode conductive agent can be also contained in above-mentioned negative electrode material.The cathode conductive agent does not have
There is special limitation, can be the cathode conductive agent of this field routine, such as carbon black, acetylene black, furnace black, carbon fiber VGCF, conduction
One of carbon black and electrically conductive graphite are a variety of.The dosage of the cathode conductive agent is known to those skilled in the art.For example,
In the negative electrode material, on the basis of the negative electrode active material content, the content of the cathode conductive agent is 0.5-10wt%.
The type and content of the third adhesive are known to those skilled in the art, such as the third binder
Selected from polythiophene, polypyrrole, polytetrafluoroethylene (PTFE), Kynoar, polyethylene, polypropylene, polystyrene, polyacrylamide, second
The propylene diene copolymerized resin of alkene-, styrene butadiene ribber, polybutadiene, fluorubber, Pluronic F-127, polyvinylpyrrolidine
Ketone, polyester resin, acrylic resin, phenolic resin, epoxy resin, polyvinyl alcohol, carboxy-propyl cellulose, ethyl cellulose, carboxylic
One of sodium carboxymethylcellulose pyce, styrene-butadiene latex are a variety of.The dosage of the third adhesive by those skilled in the art public affairs
Know.For example, on the basis of the negative electrode active material content, the content of the third adhesive is in the negative electrode material
0.01-10wt%.
According to the present invention, also there is electrolyte between above-mentioned anode and cathode.Specifically, the electrolyte includes no electromechanics
Solve matter layer and the polyelectrolyte floor positioned at the inorganic electrolyte layer surface；The inorganic electrolyte layer is located at the anode
Surface, the polyelectrolyte floor are located at the negative terminal surface.
For above-mentioned inorganic electrolyte layer, under preferable case, lithium ion conductivity is higher than 10-8S/cm, electronic conductivity
Lower than 10-9S/cm, in the preferred case, the lithium ion conductivity of the inorganic electrolyte layer are 10-2-10-7S/cm, electronics electricity
Conductance is 10-10-10-14S/cm.The lithium ion of positive electrode surface can be quickly transferred to by higher ionic conductivity in charging
Cathode；Lower electronic conductivity reduces electricity on the basis of not influencing electronic conductance between active material and collector simultaneously
The side reaction for solving liquid, improves the safety of battery.
It is understood that the migration velocity of lithium ion effectively can be improved, while reducing the object of electrolyte side reaction
Matter is used equally for as inorganic electrolyte layer of the invention.The inorganic electrolyte layer can be obtained by inorganic electrolyte particle preparation
It arrives.Specifically, above-mentioned inorganic electrolyte particle is NASICON type inorganic electrolyte and/or Ca-Ti ore type inorganic electrolyte.
According to the present invention, the NASICON type inorganic electrolyte is LiM2(PO4)3And its one of dopant or more
Kind, wherein M is selected from Ti, Zr, Ge, Sn or Pb.
For LiM2(PO4)3Dopant, the doped chemical in the dopant be selected from Mg, Ca, Sr, Ba, Sc, Al, Ga,
One of In, Nb, Ta, V or a variety of.
The Ca-Ti ore type inorganic electrolyte has following composition: AxByTiO3、AxByTa2O6、AxByNb2O6Or
AhMkDnTiwO3；Wherein 2,0 < y < 2/3 of x+3y=2, h+2k+5n+4w=6,0 < x <, h, k, n, w are all larger than 0；A be selected from Li,
One of Na element is a variety of, and B is selected from one of La, Ce, Pr, Y, Sc, Nd, Sm, Eu, Gd element or a variety of, and M is selected from
One of Sr, Ca, Ba, Ir, Pt element is a variety of, and D is selected from one of Nb, Ta element or a variety of.
Above-mentioned NASICON type inorganic electrolyte and Ca-Ti ore type inorganic electrolyte can be commercially available, can also be voluntarily
It is prepared.
According to preparation method difference, inorganic electrolyte layer can be the sheet of hard, for example, the inorganic electrolyte layer
It is the potsherd for including NASICON type inorganic electrolyte and/or Ca-Ti ore type inorganic electrolyte.
Alternatively, above-mentioned inorganic electrolyte layer may include first binder and above-mentioned inorganic electrolyte particle.
In the present invention, the first binder is selected from polythiophene, polypyrrole, polytetrafluoroethylene (PTFE), Kynoar, poly- second
Alkene, polypropylene, polystyrene, polyacrylamide, Ethylene-Propylene-Diene copolymer resins, styrene butadiene ribber, polybutadiene
Alkene, Pluronic F-127, polyvinylpyrrolidone, polyester resin, acrylic resin, phenolic resin, epoxy resin, gathers fluorubber
One of vinyl alcohol, carboxy-propyl cellulose, ethyl cellulose, polyethylene glycol oxide, sodium carboxymethylcellulose, styrene-butadiene latex are more
Kind.
According to the present invention, above-mentioned first binder is for bonding granular inorganic electrolyte particle to form integral layer
Shape, the concrete content of first binder can the specific substance according to selected by inorganic electrolyte particle it is different and different.It is preferred that feelings
Under condition, in the inorganic electrolyte layer, on the basis of the weight of the inorganic electrolyte particle, the content of the first binder
For 0.5-20wt%.
For the thickness of above-mentioned inorganic electrolyte layer, can specifically change in a big way, it is described inorganic under preferable case
Electrolyte layer with a thickness of 50-600 μm.
In the present invention, inorganic electrolyte layer surface has polyelectrolyte floor.Above-mentioned polyelectrolyte floor can be
Polyelectrolyte floor known to field of batteries, specifically, the polyelectrolyte floor includes gel polymer electrolyte
Or full solid state polymer electrolyte.
For example, specifically including thin polymer film for above-mentioned gel polymer electrolyte；The polymer thin membrane material choosing
From Kynoar, Kynoar-hexafluoropropene, polyacrylonitrile, polytetrafluoroethylene (PTFE), polymethyl methacrylate, poly- methyl
Ethyl acrylate, polyethylene glycol double maleic acid monoester, polystyrene, polyoxyethylene, polyimides, acrylic resin, asphalt mixtures modified by epoxy resin
One or more of rouge.
When in the battery carry out in use, being also adsorbed with electrolyte in above-mentioned thin polymer film.Electrolysis used by this time
Liquid can be electrolyte commonly used in the art, specifically, the electrolyte includes non-aqueous organic solvent and lithium salts, described non-aqueous have
Solvent be selected from ethylene carbonate, propene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate,
Vinylene carbonate, vinylethylene carbonate, 1,3- sulfonic acid propiolactone, 1,4- sulfonic acid butyrolactone, chlorocarbonic acid vinyl acetate, chloro
Propene carbonate, dichloro- propene carbonate, three chloro propene carbonates, fluorinated ethylene carbonate, fluoropropylene carbonate, two
One of fluoropropylene carbonate, three fluoropropylene carbonates are a variety of.
The lithium salts can use the various lithium salts made an addition in electrolyte commonly used in the art, specifically, the lithium
Salt is selected from lithium hexafluoro phosphate, LiBF4, lithium perchlorate, hexafluoroarsenate lithium, hexafluorosilicic acid lithium, di-oxalate lithium borate, chlorination
Lithium, lithium bromide, LiCF3SO3、LiC(CF3SO2)3、LiB(C2O4)2、Li2Al(CSO3Cl4)、LiP(C6H4O2)3、LiPF3
(C2F5)3、LiN(CF3SO2)2、LiN(SiC3H9)2One of or it is a variety of.
In the electrolyte, the concentration of lithium salts can change in a big way, under preferable case, the concentration of the lithium salts
For 0.5-2.0mol/L.
According to the present invention, in order to increase the conductivity of polyelectrolyte floor, under preferable case, the polymer dielectric
It further include inorganic nanoparticles in layer；The inorganic nanoparticles are selected from nanoscale TiO2、SiO2、Al2O3、ZrO2One of
Or it is a variety of.The specific additive amount of inorganic nanoparticles can change in a big way, under preferable case, the polymer dielectric
In layer, on the basis of the weight of the thin polymer film, the content of the inorganic nanoparticles is 0.5-90wt%.
For above-mentioned polyelectrolyte floor, thickness can change in a big way, under preferable case, the polymer
Electrolyte layer with a thickness of 2-100 μm.
Meanwhile the present invention also provides the preparation method of above-mentioned high pressure lithium battery electric core, specifically including will be stacked gradually
Anode, inorganic electrolyte layer, thin polymer film, cathode compression moulding, then adsorb electrolyte in thin polymer film；Form packet
Include the high pressure lithium battery electric core of anode, inorganic electrolyte layer, polyelectrolyte floor and cathode.In above-mentioned preparation method,
Above-mentioned polymer can be obtained after thin polymer film adsorbs electrolyte in precursor of the thin polymer film as polyelectrolyte floor
Electrolyte layer.
For above-mentioned preparation method, according to anode, the inorganic electrolyte layer, thin polymer film, cathode multilayer for forming stacking
The sequence of structure is different, and preparation method can be different.
According to the present invention, can be initially formed the first complex with double-layer structure, first complex include anode with
And the inorganic electrolyte layer positioned at positive electrode surface.
In the present invention, when forming above-mentioned first complex, anode can be first obtained, inorganic electrolyte is then prepared on anode
Layer；It can also be initially formed inorganic electrolyte layer, then the preparation of inorganic electrolyte layer surface is positive again.
In the following, the method for then preparing inorganic electrolyte layer on anode is described in detail to anode is first obtained.
Firstly, obtaining anode, the anode includes plus plate current-collecting body and the positive electrode positioned at plus plate current-collecting body surface.
Above-mentioned anode can be directly acquired or voluntarily be prepared.When voluntarily preparing, specific preparation method is well known to those skilled in the art
, such as anode sizing agent is coated on plus plate current-collecting body, it is prepared through drying, calendering.Wherein, anode sizing agent includes anode
Active material, conductive agent, the second binder and positive solvent.
Substance used by above-mentioned positive active material, conductive agent, the second binder and respective additive amount are as above
Described, details are not described herein.Above-mentioned anode solvent is used to for positive active material, conductive agent, the second binder being distributed in wherein,
Pulp-like is formed, coating is conducive to.In subsequent drying process, above-mentioned anode solvent is removed.It is specific used by positive solvent
Substance and additive amount be it is known to a person skilled in the art, details are not described herein.
After obtaining anode, the inorganic electrolyte layer need to be prepared on the positive electrode surface of anode.At this point, preparing the nothing
The method of machine electrolyte layer can be specifically included: using the method for coating in the positive electrode surface coating inorganic electrolyte
Then slurry is dried at 50-200 DEG C, then carry out tabletting, forms the inorganic electrolyte layer on the positive electrode surface.
Above-mentioned inorganic electrolyte slurry specifically includes first binder, inorganic electrolyte particle and the first solvent.Above-mentioned nothing
Specific substance and content used by first binder and inorganic electrolyte particle in machine electrolyte slurry as it was noted above,
This is repeated no more.For above-mentioned first solvent, for first binder, inorganic electrolyte distribution of particles in wherein, to be formed slurry
Expect shape, is conducive to coating.In subsequent drying process, above-mentioned first solvent is removed.Specific substance used by first solvent with
And additive amount be it is known to a person skilled in the art, such as first solvent be selected from water, acetone, N-Methyl pyrrolidone,
One of dimethyl sulfoxide, n,N-Dimethylformamide, ethyl alcohol are a variety of.Using the weight of the inorganic electrolyte particle as base
Standard, the content of first solvent are 20-350wt%.
Under preferable case, the inorganic electrolyte layer that is prepared by the above method with a thickness of 50-600 μm.
In the following, then the method for inorganic electrolyte layer surface preparation anode carries out in detail again to inorganic electrolyte layer is initially formed
Thin description.
Specifically, be initially formed inorganic electrolyte layer, the inorganic electrolyte layer be include NASICON type inorganic electrolyte
And/or the potsherd of Ca-Ti ore type inorganic electrolyte.
The method for forming above-mentioned potsherd can be existing sintering process, for example, inorganic electrolyte particle is pressed into
Thin slice is sintered at 800-1200 DEG C, forms the inorganic electrolyte layer.
For inorganic electrolyte particle employed in above-mentioned sintering process, specific substance is as it was noted above, herein not
It repeats again.
By control inorganic electrolyte particle additive amount, make the inorganic electrolyte layer being prepared with a thickness of 50-600
μm。
Then, positive electrode need to be formed in the inorganic electrolyte layer surface.The method for forming positive electrode can use
The existing method for forming positive electrode on plus plate current-collecting body surface, such as will be glued containing positive active material, conductive agent, second
Tie agent, the anode sizing agent of positive solvent is coated on the inorganic electrolyte layer surface, then tabletting, drying, the positive solvent of removing
?.Anode sizing agent forms as described previously.
After forming above-mentioned positive electrode, also plus plate current-collecting body need to be formed on positive electrode surface.Specifically, ability can be passed through
Commonly various methods on positive electrode surface form above-mentioned plus plate current-collecting body in domain, for example, can pass through the side of physical vapour deposition (PVD)
Formula deposits one layer of aluminium on positive electrode surface.Or plus plate current-collecting body slurry (such as aluminium paste) is coated on positive electrode surface, so
It is sintered afterwards.The above-mentioned technique for preparing plus plate current-collecting body be it is known in the art, details are not described herein.
According to the present invention, the polymer thin can be formed in the inorganic electrolyte layer surface of aforementioned the first obtained complex
Then cathode is placed in compression moulding on the thin polymer film by film.First cathode and the thin polymer film can also be formed
Second complex, then the first complex and the second complex are laminated, contact inorganic electrolyte layer and thin polymer film, then
Compression moulding.
Specifically, the inorganic electrolyte layer surface in aforementioned the first obtained complex forms the side of the thin polymer film
Method is included in the inorganic electrolyte layer surface coated polymer slurry, then dries.
The polymer paste includes polymer and the second solvent.Wherein, polymer is selected from Kynoar, polyvinylidene fluoride
Alkene-hexafluoropropene, polyacrylonitrile, polytetrafluoroethylene (PTFE), polymethyl methacrylate, polyethyl methacrylate, polyethylene glycol are double
One or more of maleic acid monoester, polystyrene, polyoxyethylene, polyimides, acrylic resin, epoxy resin.It is described
Second solvent is selected from N-Methyl pyrrolidone, water, acetone, dimethyl sulfoxide, n,N-Dimethylformamide, ethyl alcohol, tetrahydrofuran
One of or it is a variety of.
On the basis of the polymer weight, the content of second solvent is 30-2000wt%.
In the case of, according to the invention it is preferred to, the polymer paste further includes inorganic nanoparticles；The inorganic nano
Grain-by-grain seed selection is from nanoscale TiO2、SiO2、Al2O3、ZrO2One of or it is a variety of；On the basis of the polymer weight, the nothing
The content of machine nano particle is 0.5-90wt%.
Cathode is finally provided, the cathode includes negative current collector and the cathode material positioned at the negative current collector surface
Material.Specifically, above-mentioned cathode can be directly commercially available or be voluntarily prepared.For example, in general, the preparation of cathode uses this field
Technology well known to technical staff, such as may include: to mix negative electrode active material and third binder with cathode solvent, it is formed
Then negative electrode slurry is coated and/or is filled on negative current collector by negative electrode slurry, drying is rolled or do not rolled, and can be obtained
The cathode.
The specific substance and additive amount of negative electrode active material and third binder in above-mentioned negative electrode slurry as it was noted above,
Details are not described herein.N-Methyl pyrrolidone (NMP), dimethylformamide can be selected from by preparing used cathode solvent when cathode
(DMF), diethylformamide (DEF), one kind of dimethyl sulfoxide (DMSO), tetrahydrofuran (THF) and water and alcohol series solvent
Or it is a variety of.The dosage of statistics can make the paste have viscosity and mobility, can be coated to the negative current collector i.e.
It can.
Finally cathode is placed on thin polymer film, contacts negative electrode material with thin polymer film, is then pressed into type.
According to the present invention, as previously mentioned, including mentioning by the method that cathode and the thin polymer film form the second complex
For cathode, the cathode includes negative current collector and the negative electrode material positioned at the negative current collector surface.Likewise, obtaining institute
The method for stating cathode is as previously described.
After forming above-mentioned cathode, the thin polymer film need to be formed on the negative electrode material surface, to obtain with layer
Second complex of folded cathode and thin polymer film.
Specifically, being included in the cathode in the method that aforementioned obtained negative electrode material surface forms the thin polymer film
Material surface coated polymer slurry, is then dried, and obtains the thin polymer film.
The polymer paste includes polymer and the second solvent.Wherein, polymer is selected from Kynoar, polyvinylidene fluoride
Alkene-hexafluoropropene, polyacrylonitrile, polytetrafluoroethylene (PTFE), polymethyl methacrylate, polyethyl methacrylate, polyethylene glycol are double
One or more of maleic acid monoester, polystyrene, polyoxyethylene, polyimides, acrylic resin, epoxy resin.It is described
Second solvent is selected from N-Methyl pyrrolidone, water, acetone, dimethyl sulfoxide, n,N-Dimethylformamide, ethyl alcohol, tetrahydrofuran
One of or it is a variety of.
On the basis of the polymer weight, the content of second solvent is 30-2000wt%.
In the case of, according to the invention it is preferred to, the polymer paste further includes inorganic nanoparticles；The inorganic nano
Grain-by-grain seed selection is from nanoscale TiO2、SiO2、Al2O3、ZrO2One of or it is a variety of；On the basis of the polymer weight, the nothing
The content of machine nano particle is 0.5-90wt%.
In the present invention, under preferable case, the thin polymer film being prepared with a thickness of 2-100 μm.
After forming above-mentioned second complex, then the first complex and the second complex be laminated, make inorganic electrolyte layer and
Thin polymer film contact, is then pressed into type.
As previously mentioned, the present invention provides a variety of methods for forming above-mentioned high pressure lithium battery electric core, it is possible to understand that, it is above-mentioned
Various method differences are the adjustment of part steps in preparation process, the High Temperature Lithium Cell battery core performance of above-mentioned various method preparations
Substantially there is no difference.
In the present invention, the method for compression moulding above-mentioned are as follows: the hot pressing 0.05-10h at 50-300 DEG C, 0.1-50MPa.
According to the present invention, further include the steps that the thin polymer film and electrolyte contacts after the compression moulding,
Polyelectrolyte floor of the invention can be obtained after thin polymer film absorption electrolyte.
In addition, the present invention also provides a kind of lithium ion battery, including shell and it is located at the intracorporal battery core of the shell, it is described
Battery core is high pressure lithium battery electric core provided by the present invention.
The present invention is further detailed by the following examples.
Embodiment 1
The present embodiment is for illustrating high pressure lithium battery electric core disclosed by the invention and preparation method thereof.
The production of anode:
By 930 grams of positive electrode active materials LiNi0.5Mn1.5O4, 30 grams of bonding agent PVDF, 20 grams of acetylene blacks, 20g conductive agent HV
It is added in 1500 grams of solvent NMP (N-Methyl pyrrolidone), is then stirred in de-airing mixer, forming stable uniform just
Pole slurry.The anode sizing agent is equably intermittently coated on to aluminium foil (aluminium foil size are as follows: 160 millimeters of width, 16 microns of thickness)
On two sides, then 120 DEG C of drying, obtain anode after roll squeezer tabletting.
The production of first complex:
By 950 grams of inorganic electrolyte particle Li1.3Al0.3Ti1.7(PO4)3, 5 grams of binder SBR be added to 1000 grams
It in ionized water, is then stirred in de-airing mixer, forms the inorganic electrolyte slurry of stable uniform.The slurry is continuously coated with
On aforementioned positive electrode, then 120 DEG C of drying, obtain the first complex after roll squeezer tabletting.Wherein, inorganic electrolyte thickness
Degree is 60 μm.
The production of thin polymer film:
600 grams of PVDF and 200 gram of PMMA is added in 1000 grams of NMP, then heating stirring is to transparent molten
Liquid.The solution is continuously coated on the inorganic electrolyte layer of aforementioned the first obtained complex, then 80 DEG C of drying, tailoring ruler
Very little is 485 (length) × 46 (width), and 15 μm of thin polymer film is formed on the inorganic electrolyte layer of the first complex.
The production of cathode:
940 grams of negative electrode active material artificial graphites, 30 grams of bonding agent CMC and 30 grams of bonding agent SBR are added to 1200 grams
It in deionized water, is then stirred in de-airing mixer, forms the negative electrode slurry of stable uniform.The slurry is equably intermittently applied
Cloth is on the two sides of copper foil (aluminium foil size are as follows: 160 millimeters of width, 16 microns of thickness), then 120 DEG C of drying, by roll squeezer
After tabletting, cut out as the cathode having a size of 480 (length) × 45 (width).
There is the first complex alignment of thin polymer film to be placed in hot press cathode and surface, 150 DEG C of progress,
0.5MPa hot pressing 1 hour.
Above-mentioned pressed sample is subjected to fluid injection and (at this point, thin polymer film adsorbs electrolyte, forms polymer dielectric
Layer), dry, packaging, chemical conversion, lithium ion battery is made, wherein the battery core of lithium ion battery includes stacking gradually just
Pole, inorganic electrolyte layer, polyelectrolyte floor and cathode.
Embodiment 2
The present embodiment is for illustrating high pressure lithium battery electric core disclosed by the invention and preparation method thereof.
The production of anode:
By 930 grams of positive electrode active materials LiNi0.5Mn1.5O4, 30 grams of bonding agent PVDF, 20 grams of acetylene blacks, 20g conductive agent HV
It is added in 1500 grams of solvent NMP (N-Methyl pyrrolidone), is then stirred in de-airing mixer, forming stable uniform just
Pole slurry.The anode sizing agent is equably intermittently coated on to aluminium foil (aluminium foil size are as follows: 160 millimeters of width, 16 microns of thickness)
On two sides, then 120 DEG C of drying, obtain anode after roll squeezer tabletting.
The production of first complex:
By 950 grams of inorganic electrolyte particle Li0.5La0.5TiO3, 5 grams of binder SBR be added to 1000 grams of deionizations
It in water, is then stirred in de-airing mixer, forms the inorganic electrolyte slurry of stable uniform.Before the slurry is continuously coated on
It states on anode, then 120 DEG C of drying, obtain the first complex after roll squeezer tabletting.Wherein, inorganic electrolyte layer with a thickness of
50μm。
The production of thin polymer film:
600 grams of PVDF and 200 gram of PMMA is added in 1000 grams of NMP, then heating stirring is to transparent molten
Liquid.The solution is continuously coated on the inorganic electrolyte layer of aforementioned the first obtained complex, then 80 DEG C of drying, tailoring ruler
Very little is 485 (length) × 46 (width), and 20 μm of thin polymer film is formed on the inorganic electrolyte layer of the first complex.
The production of cathode:
940 grams of negative electrode active material artificial graphites, 30 grams of bonding agent CMC and 30 grams of bonding agent SBR are added to 1200 grams
It in deionized water, is then stirred in de-airing mixer, forms the negative electrode slurry of stable uniform.The slurry is equably intermittently applied
Cloth is on the two sides of copper foil (aluminium foil size are as follows: 160 millimeters of width, 16 microns of thickness), then 120 DEG C of drying, by roll squeezer
After tabletting, cut out as the cathode having a size of 480 (length) × 45 (width).
There is the first complex alignment of thin polymer film to be placed in hot press cathode and surface, 120 DEG C of progress,
2MPa hot pressing 0.5 hour.
Above-mentioned pressed sample is subjected to fluid injection and (at this point, thin polymer film adsorbs electrolyte, forms polymer dielectric
Layer), dry, packaging, chemical conversion, lithium ion battery is made, wherein the battery core of lithium ion battery includes stacking gradually just
Pole, inorganic electrolyte layer, polyelectrolyte floor and cathode.
Embodiment 3
The present embodiment is for illustrating high pressure lithium battery electric core disclosed by the invention and preparation method thereof.
The production of inorganic electrolyte layer:
By 1000 grams of inorganic electrolyte particle Li1.3Al0.3Ti1.7(PO4)3It is sintered, is formed with a thickness of 250 μ at 900 DEG C
M inorganic electrolyte layer.
The production of first complex:
By 850 grams of positive electrode active materials LiMn2O4, 80 grams of Li3PO430 grams of bonding agent polyvinylidene fluoride, 20 grams of carbon nanometers
Pipe, 20g conductive agent HV are added in 1800 grams of solvent NMP (N-Methyl pyrrolidone), are then stirred in de-airing mixer, shape
At the anode sizing agent of stable uniform.The anode sizing agent is equably intermittently coated on inorganic electrolyte layer surface.Then 120 DEG C of bakings
It is dry, positive electrode is obtained after roll squeezer tabletting.Then positive electrode surface coats aluminium paste and is sintered again, forms anode collection
Body.
The production of thin polymer film:
By 700 grams of PVDF, 300 grams of SiO2It is added in 1200 grams of NMP, then heating stirring is modulated into slurry.
The solution is continuously coated on the inorganic electrolyte layer of aforementioned the first obtained complex, then 80 DEG C of drying, cut out size
For 485 (length) × 46 (width), 8 μm of thin polymer film is formed on the inorganic electrolyte layer of the first complex.
The production of cathode:
940 grams of negative electrode active material artificial graphites, 40 grams of bonding agent polyvinyl alcohol and 40 grams of bonding agent SBR are added to
It in 1200 grams of deionized waters, is then stirred in de-airing mixer, forms the negative electrode slurry of stable uniform.Equably by the slurry
Interval is coated on the two sides of copper foil (aluminium foil size are as follows: 160 millimeters of width, 16 microns of thickness), then 120 DEG C of drying, is passed through
After roll squeezer tabletting, cut out as the cathode having a size of 480 (length) × 45 (width).
There is the first complex alignment of thin polymer film to be placed in hot press cathode and surface, 110 DEG C of progress,
2MPa hot pressing 5 hours.
Above-mentioned pressed sample is subjected to fluid injection and (at this point, thin polymer film adsorbs electrolyte, forms polymer dielectric
Layer), dry, packaging, chemical conversion, lithium ion battery is made, wherein the battery core of lithium ion battery includes stacking gradually just
Pole, inorganic electrolyte layer, polyelectrolyte floor and cathode.
Embodiment 4
The present embodiment is for illustrating high pressure lithium battery electric core disclosed by the invention and preparation method thereof.
The production of inorganic electrolyte layer:
By 1000 grams of inorganic electrolyte particle Li1.3Al0.3Ti1.7(PO4)3It is sintered, is formed with a thickness of 200 at 1100 DEG C
μm inorganic electrolyte layer.
The production of first complex:
By 850 grams of positive electrode active materials LiMn2O4, 80 grams of Li3PO430 grams of bonding agent polyvinylidene fluoride, 20 grams of carbon nanometers
Pipe, 20g conductive agent HV are added in 1800 grams of solvent NMP (N-Methyl pyrrolidone), are then stirred in de-airing mixer, shape
At the anode sizing agent of stable uniform.The anode sizing agent is equably intermittently coated on inorganic electrolyte layer surface.Then 120 DEG C of bakings
It is dry, positive electrode is obtained after roll squeezer tabletting.Then positive electrode surface coats aluminium paste and is sintered again, forms anode collection
Body.
The production of cathode:
940 grams of negative electrode active material artificial graphites, 40 grams of bonding agent polyvinyl alcohol and 40 grams of bonding agent SBR are added to
It in 1200 grams of deionized waters, is then stirred in de-airing mixer, forms the negative electrode slurry of stable uniform.Equably by the slurry
Interval is coated on the two sides of copper foil (aluminium foil size are as follows: 160 millimeters of width, 16 microns of thickness), then 120 DEG C of drying, is passed through
After roll squeezer tabletting, cut out as the cathode having a size of 480 (length) × 45 (width).
The production of second complex:
By 800 grams of PVDF, 200 grams of TiO2It is added in 1500 grams of NMP, then heating stirring is modulated into slurry.
The slurry is continuously coated on aforementioned obtained cathode, then 80 DEG C of drying, cut out having a size of 485 (length) × 46 (width),
55 μm of thin polymer film is formed on cathode.
The alignment of the inorganic electrolyte layer of the thin polymer film of second complex and the first complex is placed in hot press,
Carry out 110 DEG C, 2MPa hot pressing 5 hours.
Above-mentioned pressed sample is subjected to fluid injection and (at this point, thin polymer film adsorbs electrolyte, forms polymer dielectric
Layer), dry, packaging, chemical conversion, lithium ion battery is made, wherein the battery core of lithium ion battery includes stacking gradually just
Pole, inorganic electrolyte layer, polyelectrolyte floor and cathode.
Embodiment 5
The present embodiment is for illustrating high pressure lithium battery electric core disclosed by the invention and preparation method thereof.
The production of anode:
By 880 grams of positive electrode active materials LiCoPO4, 80 grams of LiNbO3, 3 grams of bonding agent polyvinylidene fluoride, 5 grams of carbon blacks, 5g
Conductive agent HV is added in 800 grams of solvent NMP (N-Methyl pyrrolidone), is then stirred in de-airing mixer, is formed and is stablized
Uniform anode sizing agent.The anode sizing agent is equably intermittently coated on aluminium foil (aluminium foil size are as follows: 160 millimeters of width, thickness 16
Micron) two sides on, then 120 DEG C drying, obtain anode after roll squeezer tabletting.
The production of first complex:
By 950 grams of inorganic electrolyte particle Li1.3Al0.3Ti1.7(PO4)3, 5 grams of binder polyethylene glycol oxide is added to
It in 1000 grams of deionized waters, is then stirred in de-airing mixer, forms the inorganic electrolyte slurry of stable uniform.By the slurry
It is continuously coated on aforementioned positive electrode, then 45 DEG C of drying, obtain the first complex after roll squeezer tabletting.Wherein, no electromechanics
Matter layer is solved with a thickness of 120 μm.
The production of thin polymer film:
By 600 grams of acrylic resin and 200 grams of PS, 200 grams of TiO2It is added in 1000 grams of water, modulation is slurried
Material.The slurry is continuously coated on the inorganic electrolyte layer of aforementioned the first obtained complex, then 55 DEG C of drying, tailoring ruler
Very little is 485 (length) × 46 (width), and 20 μm of thin polymer film is formed on the inorganic electrolyte layer of the first complex.
The production of cathode:
940 grams of negative electrode active material artificial graphites, 5 grams of bonding agent polytetrafluoroethylene (PTFE) are added to 1200 grams of deionized waters
In, it is then stirred in de-airing mixer, forms the negative electrode slurry of stable uniform.The slurry is equably intermittently coated on copper foil
On the two sides of (aluminium foil size are as follows: 160 millimeters of width, 16 microns of thickness), then 120 DEG C of drying, after roll squeezer tabletting, are cut
Cutting out is the cathode having a size of 480 (length) × 45 (width).
There is the first complex alignment of thin polymer film to be placed in hot press cathode and surface, 80 DEG C of progress,
10MPa hot pressing 1 hour.
Above-mentioned pressed sample is subjected to fluid injection and (at this point, thin polymer film adsorbs electrolyte, forms polymer dielectric
Layer), dry, packaging, chemical conversion, lithium ion battery is made, wherein the battery core of lithium ion battery includes stacking gradually just
Pole, inorganic electrolyte layer, polyelectrolyte floor and cathode.
Comparative example 1
This comparative example is for comparative illustration high pressure lithium battery electric core disclosed by the invention and preparation method thereof.
By the identical anode of embodiment 1, cathode and rectangular lithium ion battery is wound into a thickness of 20 μm of polypropylene diaphragm
Battery core, then after fluid injection, sealing, ageing, chemical conversion, partial volume up to this control experiment battery.
Comparative example 2
This comparative example is for comparative illustration high pressure lithium battery electric core disclosed by the invention and preparation method thereof.
The preparation method of battery is substantially the same manner as Example 1, and difference is, does not prepare polyelectrolyte floor.
Comparative example 3
This comparative example is for comparative illustration high pressure lithium battery electric core disclosed by the invention and preparation method thereof.
The preparation method of battery is substantially the same manner as Example 1, and difference is, does not prepare inorganic electrolyte layer.Performance test
The above-mentioned battery being prepared is performed the following performance tests:
The battery that each embodiment and comparative example is prepared respectively is taken 20, is examined in LAND CT2001C secondary cell performance
It surveys on device, under the conditions of 25 ± 1 DEG C, battery is subjected to charge and discharge cycles test with 0.0.1C.Steps are as follows: shelving 10min；It is permanent
Pressure charges to 5V/0.05C cut-off；Shelve 10min；Constant-current discharge is to 3.0V, as 1 time circulation.Repeat the step, cyclic process
In when battery capacity 80% lower than discharge capacity for the first time, loop termination, the cycle-index is the cycle life of battery, often
Group is averaged.
Test result is as follows:
Circulating battery 325 times of the preparation of embodiment 1；
Circulating battery 316 times of the preparation of embodiment 2；
Circulating battery 580 times of the preparation of embodiment 3；
Circulating battery 632 times of the preparation of embodiment 4；
Circulating battery 475 times of the preparation of embodiment 5；
For circulating battery prepared by comparative example 1 less than 5 times, percentage of batteries persistently produces gas to battery swell in cyclic process,
And then it catches fire；
Short circuit occurs during battery initial charge prepared by comparative example 2, voltage continuous decrease is zero, can not be followed
Ring；
For circulating battery prepared by comparative example 3 less than 10 times, percentage of batteries persistently produces gas to battery swell in cyclic process,
And then it catches fire.
By above-mentioned test it is found that high pressure lithium battery electric core provided by the invention has excellent cycle performance and safety
Can, cycle performance of battery and security performance decline caused by effectively electrolyte capable of being avoided to be oxidized.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (28)
1. a kind of high pressure lithium battery electric core, which is characterized in that including anode, cathode and the electrolysis between anode and cathode
Matter；
The electrolyte includes inorganic electrolyte layer and the polyelectrolyte floor positioned at the inorganic electrolyte layer surface；
The inorganic electrolyte layer is located at the positive electrode surface, and the polyelectrolyte floor is located at the negative terminal surface；
The inorganic electrolyte layer with a thickness of 50-600 μm, the polyelectrolyte floor with a thickness of 2-100 μm.
2. high pressure lithium battery electric core according to claim 1, which is characterized in that the inorganic electrolyte layer is to include
The potsherd of NASICON type inorganic electrolyte and/or Ca-Ti ore type inorganic electrolyte.
3. high pressure lithium battery electric core according to claim 1, which is characterized in that the inorganic electrolyte layer includes first viscous
Agent and inorganic electrolyte particle are tied, the inorganic electrolyte particle is that NASICON type inorganic electrolyte and/or Ca-Ti ore type are inorganic
Electrolyte.
4. high pressure lithium battery electric core according to claim 2 or 3, which is characterized in that the NASICON type inorganic electrolyte
For LiM2(PO4)3And its one of dopant or a variety of；
Wherein, M is selected from Ti, Zr, Ge, Sn or Pb；
Doped chemical in the dopant is selected from one of Mg, Ca, Sr, Ba, Sc, Al, Ga, In, Nb, Ta, V or a variety of；
The Ca-Ti ore type inorganic electrolyte has following composition: AxByTiO3、AxByTa2O6、AxByNb2O6Or AhMkDnTiwO3；
Wherein 2,0 < y < 2/3 of x+3y=2, h+2k+5n+4w=6,0 < x <, h, k, n, w are all larger than 0；A is in Li, Na element
One or more, B is selected from one of La, Ce, Pr, Y, Sc, Nd, Sm, Eu, Gd element or a variety of, M be selected from Sr, Ca, Ba, Ir,
One of Pt element is a variety of, and D is selected from one of Nb, Ta element or a variety of.
5. high pressure lithium battery electric core according to claim 3, which is characterized in that the first binder be selected from polythiophene,
Polypyrrole, polytetrafluoroethylene (PTFE), Kynoar, polyethylene, polypropylene, polystyrene, polyacrylamide, Ethylene-Propylene-Diene
Copolymer resins, styrene butadiene ribber, polybutadiene, fluorubber, Pluronic F-127, polyvinylpyrrolidone, polyester resin,
Acrylic resin, phenolic resin, epoxy resin, polyvinyl alcohol, carboxy-propyl cellulose, ethyl cellulose, polyethylene glycol oxide, carboxylic first
One of base sodium cellulosate, styrene-butadiene latex are a variety of.
6. high pressure lithium battery electric core according to claim 3, which is characterized in that in the inorganic electrolyte layer, with described
On the basis of the weight of inorganic electrolyte particle, the content of the first binder is 0.5-20wt%.
7. high pressure lithium battery electric core described in any one of -3,5,6 according to claim 1, which is characterized in that the polymer
Electrolyte layer includes gel polymer electrolyte or full solid state polymer electrolyte.
8. high pressure lithium battery electric core according to claim 7, which is characterized in that the gel polymer electrolyte includes poly-
The electrolyte for closing object film and being adsorbed in the thin polymer film.
9. high pressure lithium battery electric core according to claim 8, which is characterized in that the polyelectrolyte floor includes inorganic
Nano particle；The inorganic nanoparticles are selected from nanoscale TiO2、SiO2、Al2O3、ZrO2One of or it is a variety of；It is described poly-
In polymer electrolyte layer, on the basis of the weight of the thin polymer film, the content of the inorganic nanoparticles is 0.5-
90wt%.
10. high pressure lithium battery electric core described in any one of -3,5,8,9 according to claim 1, which is characterized in that it is described just
Pole includes plus plate current-collecting body and the positive electrode on plus plate current-collecting body；
The positive electrode includes positive active material；The positive active material is selected from LiNi0.5Mn1.5O4、LiMn2O4、
LiCoPO4、LiNiPO4、Li3V3(PO4)3One of or it is a variety of.
11. high pressure lithium battery electric core according to claim 10, which is characterized in that further include solid-state in the positive electrode
Electrolyte additive, the solid electrolyte additive are selected from LiNbO3、LiTaO3、Lix1La1/(3-x1)TaO3、Li3PO4、
Lix2Tiy2(PO4)3、Lix3Aly3Tiz3(PO4)3、Li2SiO3、Li2O、Li2S、Li2S-P2S5、Li2S-SiS2-P2S5、
Lix4Siy4Sz4、Lix5Py5Sz5、LiBO2、Li3.6Si0.6P0.4O4One of or it is a variety of, wherein 0 < x1 < 3；0 < x2 < 2,0
< y2 < 3；0 < x3 <, 2,0 < y3 <, 1,0 < z3 < 3；0 < x4 <, 3,0 < y4 <, 2,0 < z4 < 4；0 < x5 <, 3,0 < y5
3,0 < z5 < 7 of <.
12. high pressure lithium battery electric core according to claim 11, which is characterized in that the positive electrode, with positive-active
On the basis of the weight of substance, the content of the solid electrolyte additive is 0.1-50wt%.
13. the preparation method of high pressure lithium battery electric core as described in claim 1, which is characterized in that including what will be stacked gradually
Anode, inorganic electrolyte layer, thin polymer film, cathode compression moulding, then adsorb electrolyte in thin polymer film；Form packet
Include the high pressure lithium battery electric core of anode, inorganic electrolyte layer, polyelectrolyte floor and cathode.
14. preparation method according to claim 13, which is characterized in that before the compression moulding further include forming first
Complex, first complex include anode and the inorganic electrolyte layer positioned at positive electrode surface.
15. preparation method according to claim 14, which is characterized in that it is described formed the first complex method include:
Anode is provided, the anode includes plus plate current-collecting body and the positive electrode positioned at plus plate current-collecting body surface；Then it is described just
Pole material surface prepares the inorganic electrolyte layer.
16. preparation method according to claim 15, which is characterized in that prepared on the positive electrode surface described inorganic
The method of electrolyte layer includes: then to dry at 50-200 DEG C in the positive electrode surface coating inorganic electrolyte slurry,
Tabletting is carried out again, forms the inorganic electrolyte layer on the positive electrode surface；
The inorganic electrolyte slurry includes first binder, inorganic electrolyte particle and the first solvent；With the inorganic electrolyte
On the basis of the weight of matter particle, the content of the first binder is 0.5-20wt%, and the content of first solvent is 20-
350wt%；
The inorganic electrolyte particle is NASICON type inorganic electrolyte and/or Ca-Ti ore type inorganic electrolyte；It is described
NASICON type inorganic electrolyte is LiM2(PO4)3And its one of dopant or a variety of；
Wherein, M is selected from Ti, Zr, Ge, Sn or Pb；
The Ca-Ti ore type inorganic electrolyte has following composition: AxByTiO3、AxByTa2O6、AxByNb2O6Or AhMkDnTiwO3；
Wherein 2,0 < y < 2/3 of x+3y=2, h+2k+5n+4w=6,0 < x <, h, k, n, w are all larger than 0；A is in Li, Na element
One or more, B is selected from one of La, Ce, Pr, Y, Sc, Nd, Sm, Eu, Gd element or a variety of, M be selected from Sr, Ca, Ba, Ir,
One of Pt element is a variety of, and D is selected from one of Nb, Ta element or a variety of；
The first binder is selected from polythiophene, polypyrrole, polytetrafluoroethylene (PTFE), Kynoar, polyethylene, polypropylene, polyphenyl
Ethylene, polyacrylamide, Ethylene-Propylene-Diene copolymer resins, styrene butadiene ribber, polybutadiene, fluorubber, polycyclic
Ethylene oxide, polyvinylpyrrolidone, polyester resin, acrylic resin, phenolic resin, epoxy resin, polyvinyl alcohol, carboxylic propyl are fine
Tie up one of element, ethyl cellulose, polyethylene glycol oxide, sodium carboxymethylcellulose, styrene-butadiene latex or a variety of；
First solvent is in water, acetone, N-Methyl pyrrolidone, dimethyl sulfoxide, n,N-Dimethylformamide, ethyl alcohol
It is one or more.
17. preparation method according to claim 14, which is characterized in that it is described formed the first complex method include:
Inorganic electrolyte layer is provided, the inorganic electrolyte layer is to include NASICON type inorganic electrolyte and/or Ca-Ti ore type without electromechanics
Solve the potsherd of matter；Then positive electrode is formed in the inorganic electrolyte layer surface, then is formed just on the positive electrode
Pole collector.
18. preparation method according to claim 17, which is characterized in that by inorganic electrolyte particle at 800-1200 DEG C
Sintering, forms the inorganic electrolyte layer；
The inorganic electrolyte particle is NASICON type inorganic electrolyte and/or Ca-Ti ore type inorganic electrolyte；It is described
NASICON type inorganic electrolyte is LiM2(PO4)3And its one of dopant or a variety of；
Wherein, M is selected from Ti, Zr, Ge, Sn or Pb；
Doped chemical in the dopant is selected from one of Mg, Ca, Sr, Ba, Sc, Al, Ga, In, Nb, Ta, V or a variety of；
The Ca-Ti ore type inorganic electrolyte has following composition: AxByTiO3、AxByTa2O6、AxByNb2O6Or AhMkDnTiwO3；
Wherein 2,0 < y < 2/3 of x+3y=2, h+2k+5n+4w=6,0 < x <, h, k, n, w are all larger than 0；A is in Li, Na element
One or more, B is selected from one of La, Ce, Pr, Y, Sc, Nd, Sm, Eu, Gd element or a variety of, M be selected from Sr, Ca, Ba, Ir,
One of Pt element is a variety of, and D is selected from one of Nb, Ta element or a variety of.
19. preparation method according to claim 17, which is characterized in that described to form anode in inorganic electrolyte layer surface
The method of material includes: to coat anode sizing agent, and tabletting, drying in inorganic electrolyte layer surface；
The method for forming plus plate current-collecting body is to be vapor-deposited or coat plus plate current-collecting body slurry and be sintered.
20. preparation method described in any one of 4-19 according to claim 1, which is characterized in that it is multiple to be included in described first
Fit inorganic electrolyte layer surface forms the thin polymer film, and then cathode is placed on the thin polymer film and is pressed into
Type.
21. preparation method according to claim 20, which is characterized in that form the polymerization in inorganic electrolyte layer surface
The method of object film are as follows: in the inorganic electrolyte layer surface coated polymer slurry, then dry；
The polymer paste includes polymer and the second solvent, on the basis of the polymer weight, second solvent
Content is 30-2000wt%；
The polymer is selected from Kynoar, Kynoar-hexafluoropropene, polyacrylonitrile, polytetrafluoroethylene (PTFE), poly- methyl-prop
E pioic acid methyl ester, polyethyl methacrylate, polyethylene glycol double maleic acid monoester, polystyrene, polyoxyethylene, polyimides, third
One or more of olefin(e) acid resin, epoxy resin；Second solvent is selected from N-Methyl pyrrolidone, water, acetone, dimethyl
One of sulfoxide, n,N-Dimethylformamide, ethyl alcohol, tetrahydrofuran are a variety of.
22. preparation method according to claim 21, which is characterized in that the polymer paste further includes inorganic nano
Grain；The inorganic nanoparticles are selected from nanoscale TiO2、SiO2、Al2O3、ZrO2One of or it is a variety of；
On the basis of the polymer weight, the content of the inorganic nanoparticles is 0.5-90wt%.
23. preparation method described in any one of 4-19 according to claim 1, which is characterized in that described including providing cathode
Cathode includes negative current collector and the negative electrode material positioned at the negative current collector surface；
Then the thin polymer film is formed on the negative electrode material surface, obtained with the cathode and thin polymer film being laminated
Second complex；
The first complex and the second complex are laminated again, inorganic electrolyte layer and thin polymer film is contacted, is then pressed into
Type.
24. preparation method according to claim 23, which is characterized in that form the polymer thin on negative electrode material surface
The method of film are as follows: in the negative electrode material surface coated polymer slurry, then dry；
The polymer paste includes polymer and the second solvent, on the basis of the polymer weight, second solvent
Content is 30-2000wt%；
The polymer is selected from Kynoar, Kynoar-hexafluoropropene, polyacrylonitrile, polytetrafluoroethylene (PTFE), poly- methyl-prop
E pioic acid methyl ester, polyethyl methacrylate, polyethylene glycol double maleic acid monoester, polystyrene, polyoxyethylene, polyimides, third
One or more of olefin(e) acid resin, epoxy resin；Second solvent is selected from N-Methyl pyrrolidone, water, acetone, dimethyl
One of sulfoxide, n,N-Dimethylformamide, ethyl alcohol, tetrahydrofuran are a variety of.
25. preparation method according to claim 24, which is characterized in that the polymer paste further includes inorganic nano
Grain；The inorganic nanoparticles are selected from nanoscale TiO2、SiO2、Al2O3、ZrO2One of or it is a variety of；
On the basis of the polymer weight, the content of the inorganic nanoparticles is 0.5-90wt%.
26. preparation method described in any one of 3-19,21,22,24,25 according to claim 1, which is characterized in that described
The method of compression moulding are as follows: the hot pressing 0.05-10h at 50-300 DEG C, 0.1-50MPa.
27. preparation method described in any one of 3-19,21,22,24,25 according to claim 1, which is characterized in that described
Inorganic electrolyte layer with a thickness of 50-600 μm, the thin polymer film with a thickness of 2-100 μm.
28. a kind of lithium ion battery, which is characterized in that including shell and be located at the intracorporal battery core of the shell, the battery core is power
Benefit requires high pressure lithium battery electric core described in any one of 1-12.
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