CN105470576A - High voltage lithium battery cell and preparation method therefor, and lithium ion battery - Google Patents
High voltage lithium battery cell and preparation method therefor, and lithium ion battery Download PDFInfo
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- CN105470576A CN105470576A CN201410437044.0A CN201410437044A CN105470576A CN 105470576 A CN105470576 A CN 105470576A CN 201410437044 A CN201410437044 A CN 201410437044A CN 105470576 A CN105470576 A CN 105470576A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- 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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Abstract
For overcoming the problem of degradation of lithium battery performance caused by high probability of oxidization of an electrolyte of a high voltage lithium battery in the prior art, the invention provides a high voltage lithium battery cell. The high voltage lithium battery cell comprises a positive electrode, a negative electrode and an electrolyte positioned between the positive electrode and the negative electrode; the electrolyte comprises an inorganic electrolyte layer and a polymer electrolyte layer positioned on the surface of the inorganic electrolyte layer; the inorganic electrolyte layer is positioned on the surface of the positive electrode; and the polymer electrolyte layer is positioned on the surface of the negative electrode. Meanwhile, the invention also discloses a preparation method for the high voltage lithium battery cell and a lithium ion battery adopting the high voltage lithium battery cell. The high voltage lithium battery cell provided by the invention can overcome a large amount of negative problems caused by oxidization of the electrolyte, and the safety performance and the cycling performance of the lithium battery can be improved.
Description
Technical field
The invention belongs to high-voltage lithium ion battery field, particularly relate to a kind of high pressure lithium battery electric core and preparation method thereof, and adopt the high-voltage lithium ion battery of this high pressure lithium battery electric core.
Background technology
Lithium ion battery is compared with other batteries, have that quality is light, volume is little, operating voltage is high, energy density is high, power output is large, charge efficiency is high, memory-less effect, the advantage such as have extended cycle life, not only be widely used in the field such as mobile phone, notebook computer, and be considered to one of the optimal selection of electric motor car, large-scale energy storage device.But smart mobile phone at present, the electronic digital products such as panel computer require more and more higher to the energy density of battery, make commercial li-ion battery be difficult to meet the demands.High power capacity positive electrode or high-voltage anode material is adopted to be the most effective way promoting lithium ion battery energy density.
The research of current high-voltage anode material mainly focuses on LiNi
0.5mn
1.5o
4, LiCoPO
4, LiNiPO
4deng material, its discharge platform is respectively 4.7V, 4.8V and 5.1V, and charge cutoff voltage is all higher than 4.5V.High power capacity positive electrode is with rich lithium layer shape solid-solution material for study hotspot, and the prerequisite of its release high power capacity is for will be charged to more than 4.5V by material.The operating voltage of current commercial electrolyte liquid is below 4.3V, as application under more than 4.5V voltage can be oxidized, causes side reaction to increase, cycle performance of battery is poor, degradation problem under fail safe, is difficult to be applied in high pressure lithium battery.
Summary of the invention
Technical problem to be solved by this invention is oxidizable for the electrolyte of prior art mesohigh lithium battery and cause the problem of lithium battery hydraulic performance decline, provides a kind of high pressure lithium battery electric core.
It is as follows that the present invention solves the problems of the technologies described above adopted technical scheme:
A kind of high pressure lithium battery electric core is provided, comprises positive pole, negative pole and the electrolyte between positive pole and negative pole; Described electrolyte comprises inorganic electrolyte layer and is positioned at the polyelectrolyte floor on described inorganic electrolyte layer surface; Described inorganic electrolyte layer is positioned at described positive electrode surface, and described polyelectrolyte floor is positioned at described negative terminal surface.
The present invention, by arranging inorganic electrolyte layer and polyelectrolyte floor between a positive electrode and a negative electrode, can ensure positive electrode capacity normal performance under high voltages.Inorganic electrolyte layer can improve the ionic conduction ability of positive electrode on the one hand, can avoid the side reaction between electrolyte and high-voltage anode material simultaneously, effectively ensure that the performance of high pressure lithium battery.But found by great many of experiments, if inorganic electrolyte layer directly contacts with negative pole, inorganic electrolyte layer will be reduced by the negative material of electronegative potential, electrolyte electronic conductance is caused to increase and cause battery short circuit.In the present invention, also there is the problem that polyelectrolyte floor can avoid inorganic electrolyte layer to be reduced under electronegative potential between inorganic electrolyte layer and negative pole, polyelectrolyte floor ensure that the normal performance of electronegative potential capacity of negative plates, the electrolyte barrier layer each other of double-layer structure, can effectively block separately because of side reaction that potential problem is brought, ensure the high voltage of battery and high-energy-density, be beneficial to and improve the high and cycle performance of battery safety.
Meanwhile, present invention also offers the preparation method of above-mentioned high pressure lithium battery electric core, the positive pole, inorganic electrolyte layer, thin polymer film, the negative pole that comprise stacking gradually are compressing, then in thin polymer film, adsorb electrolyte; Form the described high pressure lithium battery electric core comprising positive pole, inorganic electrolyte layer, polyelectrolyte floor and negative pole.
Present invention also offers a kind of lithium ion battery in addition, comprise housing and be positioned at the battery core of described housing, described battery core is above-mentioned high pressure lithium battery electric core.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
High pressure lithium battery electric core provided by the invention comprises positive pole, negative pole and the electrolyte between positive pole and negative pole; Described electrolyte comprises inorganic electrolyte layer and is positioned at the polyelectrolyte floor on described inorganic electrolyte layer surface; Described inorganic electrolyte layer is positioned at described positive electrode surface, and described polyelectrolyte floor is positioned at described negative terminal surface.
In the present invention, the positive pole in high pressure lithium battery electric core is not particularly limited, specifically can adopts the positive pole usually adopted in existing high pressure lithium battery.Concrete, described positive pole comprises plus plate current-collecting body and is positioned at the positive electrode on plus plate current-collecting body.
The kind of described plus plate current-collecting body has been conventionally known to one of skill in the art, such as, can be selected from aluminium foil, Copper Foil, Punching steel strip.
Above-mentioned positive electrode comprises positive active material, conductive agent and the second binding agent.Concrete, described positive active material is selected from LiNi
0.5mn
1.5o
4, LiMn
2o
4, LiCoPO
4, LiNiPO
4, Li
3v
3(PO
4)
3in one or more.
The present invention is not particularly limited described conductive agent, can be the positive conductive agent of this area routine, at least one in such as acetylene black, carbon nano-tube, HV, carbon black.Wherein, with the weight of positive active material for benchmark, the content of described conductive agent is 0.1-20wt%, is preferably 1-10wt%.
The kind of described second binding agent and content are conventionally known to one of skill in the art, and such as fluorine resin and polyolefin compound are as one or more in polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE) and butadiene-styrene rubber (SBR).In general, according to the difference of adhesive therefor kind, with the weight of positive active material for benchmark, the content of the second binding agent is 0.01-10wt%, is preferably 0.02-5wt%.
In the present invention, under preferable case, also comprise solid electrolyte additive in described positive electrode, described solid electrolyte additive is selected from LiNbO
3, LiTaO
3, Li
x1la
1/ (3-x1)taO
3, Li
3pO
4, Li
x2ti
y2(PO
4)
3, Li
x3al
y3ti
z3(PO
4)
3, Li
2siO
3, Li
2o, Li
2s, Li
2s-P
2s
5, Li
2s-SiS
2-P
2s
5, Li
x4si
y4s
z4, Li
x5p
y5s
z5, LiBO
2, Li
3.6si
0.6p
0.4o
4in one or more, wherein, 0 < x
1< 3; 0 < x
2< 2,0 < y
2< 3; 0 < x
3< 2,0 < y
3< 1,0 < z
3< 3; 0 < x
4< 3,0 < y
4< 2,0 < z
4< 4; 0 < x
5< 3,0 < y
5< 3,0 < z
5< 7.
When also containing above-mentioned solid electrolyte additive in positive electrode, described high pressure lithium battery electric core has better cycle performance under high power charging-discharging condition.
The content of above-mentioned solid electrolyte additive can change in a big way, those skilled in the art can regulate according to actual conditions, under preferable case, with the weight of positive active material for benchmark, the content of solid electrolyte additive is 0.1-50wt%, is preferably 0.5-20wt%.
According to the present invention, the negative pole in above-mentioned high pressure lithium battery electric core is not particularly limited, and specifically can adopt the negative pole usually adopted in existing high pressure lithium battery.Concrete, described negative pole comprises negative current collector and is positioned at the negative material on described negative current collector.
The various negative current collectors that described negative current collector is known to the skilled person, such as, can be selected from one or more in aluminium foil, Copper Foil, nickel plated steel strip, Punching steel strip.
Described negative material comprises negative electrode active material and the 3rd binding agent.
Described negative electrode active material is not particularly limited, and can use embedding and disengaging the negative electrode active material of lithium of this area routine.Concrete, described negative active core-shell material be selected from material with carbon element, ashbury metal, silicon alloy, silicon, tin, germanium one or more.For above-mentioned material with carbon element, specifically can be selected from native graphite, natural modified graphite, Delanium, petroleum coke, organic cracking carbon, carbonaceous mesophase spherules, carbon fiber, ashbury metal and silicon alloy one or more, preferred Delanium and natural modified graphite.
Usually, according to actual conditions, in above-mentioned negative material, also cathode conductive agent can be contained.Described cathode conductive agent is not particularly limited, and can be the cathode conductive agent of this area routine, such as, in carbon black, acetylene black, furnace black, carbon fiber VGCF, conductive black and electrically conductive graphite one or more.The consumption of described cathode conductive agent is conventionally known to one of skill in the art.Such as, in described negative material, with described negative electrode active material content for benchmark, the content of described cathode conductive agent is 0.5-10wt%.
Kind and the content of the 3rd described adhesive are conventionally known to one of skill in the art, such as described 3rd binding agent is selected from polythiophene, polypyrrole, polytetrafluoroethylene, Kynoar, polyethylene, polypropylene, polystyrene, polyacrylamide, Ethylene-Propylene-Diene copolymer resins, styrene butadiene ribber, polybutadiene, fluorubber, Pluronic F-127, polyvinylpyrrolidone, mylar, acrylic resin, phenolic resins, epoxy resin, polyvinyl alcohol, carboxy-propyl cellulose, ethyl cellulose, sodium carboxymethylcellulose, one or more in styrene-butadiene latex.The consumption of described 3rd adhesive is conventionally known to one of skill in the art.Such as, in described negative material, with described negative electrode active material content for benchmark, the content of described 3rd adhesive is 0.01-10wt%.
According to the present invention, between above-mentioned positive pole and negative pole, also there is electrolyte.Concrete, described electrolyte comprises inorganic electrolyte layer and is positioned at the polyelectrolyte floor on described inorganic electrolyte layer surface; Described inorganic electrolyte layer is positioned at described positive electrode surface, and described polyelectrolyte floor is positioned at described negative terminal surface.
For above-mentioned inorganic electrolyte layer, under preferable case, its lithium ion conductivity is higher than 10
-8s/cm, electronic conductivity is lower than 10
-9s/cm, in the preferred case, the lithium ion conductivity of described inorganic electrolyte layer is 10
-2-10-
7s/cm, electronic conductivity is 10
-10-10
-14s/cm.The lithium ion of positive electrode surface can be quickly transferred to negative pole when charging by higher ionic conductivity; Lower electronic conductivity reduces the side reaction of electrolyte on the basis not affecting electronic conductance between active material and collector simultaneously, improves the fail safe of battery.
Be understandable that, effectively can improve the migration velocity of lithium ion, the material simultaneously reducing electrolyte side reaction all can be used for as inorganic electrolyte layer of the present invention.This inorganic electrolyte layer prepares by inorganic electrolyte particle.Concrete, above-mentioned inorganic electrolyte particle is NASICON type inorganic electrolyte and/or Ca-Ti ore type inorganic electrolyte.
According to the present invention, described NASICON type inorganic electrolyte is LiM
2(PO
4)
3and one or more in alloy, wherein, M is selected from Ti, Zr, Ge, Sn or Pb.
For LiM
2(PO
4)
3alloy, the doped chemical in described alloy be selected from Mg, Ca, Sr, Ba, Sc, Al, Ga, In, Nb, Ta, V one or more.
Described Ca-Ti ore type inorganic electrolyte has following composition: A
xb
ytiO
3, A
xb
yta
2o
6, A
xb
ynb
2o
6, or A
hm
kd
nti
wo
3; Wherein x+3y=2, h+2k+5n+4w=6,0 < x < 2,0 < y < 2/3, h, k, n, w are all greater than 0; A be selected from Li, Na element one or more, B be selected from La, Ce, Pr, Y, Sc, Nd, Sm, Eu, Gd element one or more, M be selected from Sr, Ca, Ba, Ir, Pt element one or more, D be selected from Nb, Ta element one or more.
Above-mentioned NASICON type inorganic electrolyte and Ca-Ti ore type inorganic electrolyte, all by commercially available, also can prepare voluntarily.
Different according to its preparation method, inorganic electrolyte layer can be the sheet of hard, and such as, described inorganic electrolyte layer is the potsherd comprising NASICON type inorganic electrolyte and/or Ca-Ti ore type inorganic electrolyte.
Or above-mentioned inorganic electrolyte layer can comprise the first binding agent and above-mentioned inorganic electrolyte particle.
In the present invention, described first binding agent be selected from polythiophene, polypyrrole, polytetrafluoroethylene, Kynoar, polyethylene, polypropylene, polystyrene, polyacrylamide, Ethylene-Propylene-Diene copolymer resins, styrene butadiene ribber, polybutadiene, fluorubber, Pluronic F-127, polyvinylpyrrolidone, mylar, acrylic resin, phenolic resins, epoxy resin, polyvinyl alcohol, carboxy-propyl cellulose, ethyl cellulose, polyethylene glycol oxide, sodium carboxymethylcellulose, styrene-butadiene latex one or more.
According to the present invention, above-mentioned first binding agent is used for granular inorganic electrolyte particle bond to form overall stratiform, the concrete content of the first binding agent can concrete material selected by inorganic electrolyte particle different and different.Under preferable case, in described inorganic electrolyte layer, with the weight of described inorganic electrolyte particle for benchmark, the content of described first binding agent is 0.5-20wt%.
For the thickness of above-mentioned inorganic electrolyte layer, specifically can change in a big way, under preferable case, the thickness of described inorganic electrolyte layer is 50-600 μm.
In the present invention, inorganic electrolyte layer surface has polyelectrolyte floor.Above-mentioned polyelectrolyte floor can polyelectrolyte floor known by field of batteries, and concrete, described polyelectrolyte floor comprises gel polymer electrolyte or full solid state polymer electrolyte.
Such as, for above-mentioned gel polymer electrolyte, specifically thin polymer film is comprised; Described polymer thin membrane material is selected from one or more in Kynoar, Kynoar-hexafluoropropylene, polyacrylonitrile, polytetrafluoroethylene, polymethyl methacrylate, polyethyl methacrylate, the two maleic mono-ester of polyethylene glycol, polystyrene, polyoxyethylene, polyimides, acrylic resin, epoxy resin.
When using in the battery, in above-mentioned thin polymer film, be also adsorbed with electrolyte.The electrolyte that now adopted electrolyte can be commonly used for this area, concrete, described electrolyte comprises non-aqueous organic solvent and lithium salts, described non-aqueous organic solvent is 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, chlorocarbonic acid propylene, dichloro-propene carbonate, three chloro propene carbonates, fluorinated ethylene carbonate, fluoropropylene carbonate, two fluoropropylene carbonates, one or more in three fluoropropylene carbonates.
Described lithium salts can adopt the various lithium salts made an addition in electrolyte conventional in this area, concrete, described lithium salts is selected from lithium hexafluoro phosphate, LiBF4, lithium perchlorate, hexafluoroarsenate lithium, hexafluorosilicic acid lithium, di-oxalate lithium borate, lithium chloride, lithium bromide, LiCF
3sO
3, LiC (CF
3sO
2)
3, LiB (C
2o
4)
2, Li
2al (CSO
3cl
4), LiP (C
6h
4o
2)
3, LiPF
3(C
2f
5)
3, LiN (CF
3sO
2)
2, LiN (SiC
3h
9)
2in one or more.
In described electrolyte, the concentration of lithium salts can change in a big way, and under preferable case, the concentration of described lithium salts is 0.5-2.0mol/L.
According to the present invention, in order to increase the conductivity of polyelectrolyte floor, under preferable case, in described polyelectrolyte floor, also comprise inorganic nanoparticles; Described inorganic nanoparticles is selected from nano level TiO
2, SiO
2, Al
2o
3, ZrO
2in one or more.The concrete addition of inorganic nanoparticles can change in a big way, and under preferable case, in described polyelectrolyte floor, with the weight of described thin polymer film for benchmark, the content of described inorganic nanoparticles is 0.5-90wt%.
For above-mentioned polyelectrolyte floor, its thickness can change in a big way, and under preferable case, the thickness of described polyelectrolyte floor is 2-100 μm.
Meanwhile, present invention also offers the preparation method of above-mentioned high pressure lithium battery electric core, the positive pole, inorganic electrolyte layer, thin polymer film, the negative pole that specifically comprise stacking gradually are compressing, then in thin polymer film, adsorb electrolyte; Form the described high pressure lithium battery electric core comprising positive pole, inorganic electrolyte layer, polyelectrolyte floor and negative pole.In above-mentioned preparation method, thin polymer film, as the precursor of polyelectrolyte floor, can obtain above-mentioned polyelectrolyte floor after thin polymer film adsorbs electrolyte.
For above-mentioned preparation method, according to the order difference forming stacked positive pole, inorganic electrolyte layer, thin polymer film, negative pole sandwich construction, preparation method can be different.
According to the present invention, first can be formed and have double-deck first complex, described first complex comprises positive pole and is positioned at the inorganic electrolyte layer of positive electrode surface.
In the present invention, when forming above-mentioned first complex, first can obtain positive pole, then on positive pole, prepare inorganic electrolyte layer; Also can first form inorganic electrolyte layer, and then positive pole is prepared on inorganic electrolyte layer surface.
Below, to first obtaining positive pole, the method then preparing inorganic electrolyte layer on positive pole is described in detail.
First, obtain positive pole, described positive pole comprises plus plate current-collecting body and is positioned at the positive electrode of anode collection surface.Above-mentioned positive pole can directly obtain or prepare voluntarily.When preparing voluntarily, its concrete preparation method is well-known to those skilled in the art, such as, be coated on plus plate current-collecting body by anode sizing agent, and drying, calendering prepare.Wherein, anode sizing agent comprises positive active material, conductive agent, the second binding agent and positive pole solvent.
Above-mentioned positive active material, conductive agent, material that the second binding agent adopts and respective addition as mentioned before, do not repeat them here.Above-mentioned positive pole solvent is used for positive active material, conductive agent, the second binding agent to be distributed in wherein, forms pulp-like, is beneficial to coating.In follow-up dry run, above-mentioned positive pole solvent is removed.The concrete material that positive pole solvent adopts and addition are that those skilled in the art known, and do not repeat them here.
After obtaining positive pole, need at the described inorganic electrolyte layer of positive electrode surface preparation of positive pole.Now, the method preparing described inorganic electrolyte layer can adopt the method for coating, specifically comprises: at described positive electrode surface-coated inorganic electrolyte slurry, then dries at 50-200 DEG C, carry out compressing tablet again, form described inorganic electrolyte layer on described positive electrode surface.
Above-mentioned inorganic electrolyte slurry specifically comprises the first binding agent, inorganic electrolyte particle and the first solvent.The concrete material that the first binding agent in above-mentioned inorganic electrolyte slurry and inorganic electrolyte particle adopt and content as mentioned before, do not repeat them here.For above-mentioned first solvent, for by the first binding agent, inorganic electrolyte distribution of particles in wherein, form pulp-like, be beneficial to coating.In follow-up dry run, above-mentioned first solvent is removed.The concrete material that first solvent adopts and addition are that those skilled in the art known, such as described first solvent be selected from water, acetone, one or more in 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), DMF, ethanol.With the weight of described inorganic electrolyte particle for benchmark, the content of described first solvent is 20-350wt%.
Under preferable case, the thickness of the inorganic electrolyte layer prepared by said method is 50-600 μm.
Below, to first forming inorganic electrolyte layer, and then the surperficial method preparing positive pole of inorganic electrolyte layer is described in detail.
Concrete, first form inorganic electrolyte layer, described inorganic electrolyte layer is the potsherd comprising NASICON type inorganic electrolyte and/or Ca-Ti ore type inorganic electrolyte.
The method forming above-mentioned potsherd can for existing sintering process, and such as, inorganic electrolyte particle being pressed into thin slice at 800-1200 DEG C sinters, and forms described inorganic electrolyte layer.
For the inorganic electrolyte particle adopted in above-mentioned sintering process, its concrete material as mentioned before, does not repeat them here.
By controlling the addition of inorganic electrolyte particle, the thickness of the inorganic electrolyte layer prepared is made to be 50-600 μm.
Then, positive electrode need be formed on described inorganic electrolyte layer surface.The method forming positive electrode can adopt the existing method forming positive electrode in anode collection surface, such as the anode sizing agent containing positive active material, conductive agent, the second binding agent, positive pole solvent is coated on described inorganic electrolyte layer surface, then compressing tablet, oven dry, removing positive pole solvent.The composition of anode sizing agent as described previously.
After forming above-mentioned positive electrode, also need form plus plate current-collecting body on positive electrode surface.Concrete, the various methods conventional by this area form above-mentioned plus plate current-collecting body on positive electrode surface, such as, by the mode of physical vapour deposition (PVD) at positive electrode surface deposition one deck aluminium.Or at positive electrode surface-coated plus plate current-collecting body slurry (such as aluminium paste), then sinter.The above-mentioned technique preparing plus plate current-collecting body is known in the art, does not repeat them here.
According to the present invention, described thin polymer film can be formed on the inorganic electrolyte layer surface of aforementioned the first complex obtained, then negative pole is placed on described thin polymer film compressing.Also first negative pole and described thin polymer film can be formed the second complex, then by the first complex and the second complex stacked, inorganic electrolyte layer is contacted with thin polymer film, then compressing.
Concrete, the method forming described thin polymer film on the inorganic electrolyte layer surface of aforementioned the first complex obtained is included in described inorganic electrolyte layer surface-coated polymer paste, then dries.
Described polymer paste comprises polymer and the second solvent.Wherein, polymer is selected from one or more in Kynoar, Kynoar-hexafluoropropylene, polyacrylonitrile, polytetrafluoroethylene, polymethyl methacrylate, polyethyl methacrylate, the two maleic mono-ester of polyethylene glycol, polystyrene, polyoxyethylene, polyimides, acrylic resin, epoxy resin.Described second solvent be selected from 1-METHYLPYRROLIDONE, water, acetone, dimethyl sulfoxide (DMSO), DMF, ethanol, oxolane one or more.
With described polymer weight for benchmark, the content of described second solvent is 30-2000wt%.
According to the present invention, under preferable case, described polymer paste also comprises inorganic nanoparticles; Described inorganic nanoparticles is selected from nano level TiO
2, SiO
2, Al
2o
3, ZrO
2in one or more; With described polymer weight for benchmark, the content of described inorganic nanoparticles is 0.5-90wt%.
Finally provide negative pole, described negative pole comprises negative current collector and is positioned at the negative material of described negative pole currect collecting surface.Concrete, above-mentioned negative pole can be directly commercially available or prepare voluntarily.Such as, in general, the preparation of negative pole adopts and well known to a person skilled in the art technology, such as can comprise: by negative electrode active material and the 3rd binding agent and negative pole solvent, form cathode size, then by cathode size coating and/or be filled on negative current collector, dry, calendering or do not roll, can obtain described negative pole.
The concrete material of the negative electrode active material in above-mentioned cathode size and the 3rd binding agent and addition as mentioned before, do not repeat them here.The negative pole solvent used when preparing negative pole can be selected from 1-METHYLPYRROLIDONE (NMP), dimethylformamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF) and water and alcohol series solvent one or more.The consumption of statistics can make described pastel have viscosity and mobility, can be coated to described negative current collector.
Finally negative pole is placed on thin polymer film, negative material is contacted with thin polymer film, then compressing.
According to the present invention, as previously mentioned, method negative pole and described thin polymer film being formed the second complex comprises provides negative pole, and described negative pole comprises negative current collector and is positioned at the negative material of described negative pole currect collecting surface.Same, obtain the method for described negative pole as previously mentioned.
After forming above-mentioned negative pole, described thin polymer film need be formed on described negative material surface, thus obtain second complex with stacked negative pole and thin polymer film.
Concrete, the method forming described thin polymer film on the aforementioned negative material surface obtained is included in described negative material surface-coated polymer paste, then dries, obtains described thin polymer film.
Described polymer paste comprises polymer and the second solvent.Wherein, polymer is selected from one or more in Kynoar, Kynoar-hexafluoropropylene, polyacrylonitrile, polytetrafluoroethylene, polymethyl methacrylate, polyethyl methacrylate, the two maleic mono-ester of polyethylene glycol, polystyrene, polyoxyethylene, polyimides, acrylic resin, epoxy resin.Described second solvent be selected from 1-METHYLPYRROLIDONE, water, acetone, dimethyl sulfoxide (DMSO), DMF, ethanol, oxolane one or more.
With described polymer weight for benchmark, the content of described second solvent is 30-2000wt%.
According to the present invention, under preferable case, described polymer paste also comprises inorganic nanoparticles; Described inorganic nanoparticles is selected from nano level TiO
2, SiO
2, Al
2o
3, ZrO
2in one or more; With described polymer weight for benchmark, the content of described inorganic nanoparticles is 0.5-90wt%.
In the present invention, under preferable case, described in the thickness of thin polymer film for preparing be 2-100 μm.
After forming above-mentioned second complex, then by the first complex and the second complex stacked, inorganic electrolyte layer is contacted with thin polymer film, then compressing.
As previously mentioned, the invention provides the method for the above-mentioned high pressure lithium battery electric core of multiple formation, understandable, above-mentioned various method difference is the adjustment of part steps in preparation technology, and High Temperature Lithium Cell battery core performance prepared by above-mentioned various method does not have difference substantially.
In the present invention, aforesaid compressing method is: at 50-300 DEG C, hot pressing 0.05-10h under 0.1-50MPa.
According to the present invention, described compressing after also comprise step by described thin polymer film and electrolyte contacts, polyelectrolyte floor of the present invention can be obtained after thin polymer film absorption electrolyte.
In addition, present invention also offers a kind of lithium ion battery, comprise housing and be positioned at the battery core of described housing, described battery core is high pressure lithium battery electric core provided by the present invention.
By the following examples the present invention is further detailed.
Embodiment 1
The present embodiment is for illustration of high pressure lithium battery electric core disclosed by the invention and preparation method thereof.
The making of positive pole:
By 930 grams of positive electrode active materials LiNi
0.5mn
1.5o
4, 30 grams of bonding agent PVDF, 20 grams of acetylene blacks, 20g conductive agent HV join in 1500 grams of solvent NMP (1-METHYLPYRROLIDONE), then stir in de-airing mixer, form the anode sizing agent of stable uniform.Intermittently be coated on the two sides of aluminium foil (aluminium foil is of a size of: width 160 millimeters, thickness 16 microns) equably by this anode sizing agent, then 120 DEG C of oven dry, obtain positive pole after roll squeezer compressing tablet.
The making of the first complex:
By the inorganic electrolyte particle Li of 950 grams
1.3al
0.3ti
1.7(PO
4)
3, the binding agent SBR of 5 grams joins in 1000 grams of deionized waters, then stir in de-airing mixer, form the inorganic electrolyte slurry of stable uniform.Be coated on continuously on aforementioned positive electrode by this slurry, then 120 DEG C of oven dry, obtain the first complex after roll squeezer compressing tablet.Wherein, inorganic electrolyte layer thickness is 60 μm.
The making of thin polymer film:
Join in the NMP of 1000 grams by the PMMA of the PVDF of 600 grams and 200 gram, then heating is stirred to transparent solution.This solution is coated on continuously on the inorganic electrolyte layer of aforementioned the first complex obtained, then 80 DEG C of oven dry, cut out and be of a size of 485 (length) × 46 (wide), the inorganic electrolyte layer of the first complex is formed the thin polymer film of 15 μm.
The making of negative pole:
940 grams of negative active core-shell material Delaniums, 30 grams of bonding agent CMC and 30 gram of bonding agent SBR are joined in 1200 grams of deionized waters, then stirs in de-airing mixer, form the cathode size of stable uniform.This slurry is intermittently coated on Copper Foil equably, and (aluminium foil is of a size of: width 160 millimeters, thickness 16 microns) two sides on, then 120 DEG C of oven dry, after roll squeezer compressing tablet, cut out the negative pole for being of a size of 480 (length) × 45 (wide).
First complex alignment negative pole and surface with thin polymer film is placed in hot press, carries out 150 DEG C, 0.5MPa hot pressing 1 hour.
Sample after above-mentioned compacting is carried out fluid injection (now, thin polymer film absorption electrolyte, form polyelectrolyte floor), dry, pack, the step such as to change into, obtained lithium ion battery, wherein the battery core of lithium ion battery comprises the positive pole, inorganic electrolyte layer, polyelectrolyte floor and the negative pole that stack gradually.
Embodiment 2
The present embodiment is for illustration of high pressure lithium battery electric core disclosed by the invention and preparation method thereof.
The making of positive pole:
By 930 grams of positive electrode active materials LiNi
0.5mn
1.5o
4, 30 grams of bonding agent PVDF, 20 grams of acetylene blacks, 20g conductive agent HV join in 1500 grams of solvent NMP (1-METHYLPYRROLIDONE), then stir in de-airing mixer, form the anode sizing agent of stable uniform.Intermittently be coated on the two sides of aluminium foil (aluminium foil is of a size of: width 160 millimeters, thickness 16 microns) equably by this anode sizing agent, then 120 DEG C of oven dry, obtain positive pole after roll squeezer compressing tablet.
The making of the first complex:
By the inorganic electrolyte particle Li of 950 grams
0.5la
0.5tiO
3, the binding agent SBR of 5 grams joins in 1000 grams of deionized waters, then stir in de-airing mixer, form the inorganic electrolyte slurry of stable uniform.Be coated on continuously on aforementioned positive electrode by this slurry, then 120 DEG C of oven dry, obtain the first complex after roll squeezer compressing tablet.Wherein, inorganic electrolyte layer thickness is 50 μm.
The making of thin polymer film:
Join in the NMP of 1000 grams by the PMMA of the PVDF of 600 grams and 200 gram, then heating is stirred to transparent solution.This solution is coated on continuously on the inorganic electrolyte layer of aforementioned the first complex obtained, then 80 DEG C of oven dry, cut out and be of a size of 485 (length) × 46 (wide), the inorganic electrolyte layer of the first complex is formed the thin polymer film of 20 μm.
The making of negative pole:
940 grams of negative active core-shell material Delaniums, 30 grams of bonding agent CMC and 30 gram of bonding agent SBR are joined in 1200 grams of deionized waters, then stirs in de-airing mixer, form the cathode size of stable uniform.This slurry is intermittently coated on Copper Foil equably, and (aluminium foil is of a size of: width 160 millimeters, thickness 16 microns) two sides on, then 120 DEG C of oven dry, after roll squeezer compressing tablet, cut out the negative pole for being of a size of 480 (length) × 45 (wide).
First complex alignment negative pole and surface with thin polymer film is placed in hot press, carries out 120 DEG C, 2MPa hot pressing 0.5 hour.
Sample after above-mentioned compacting is carried out fluid injection (now, thin polymer film absorption electrolyte, form polyelectrolyte floor), dry, pack, the step such as to change into, obtained lithium ion battery, wherein the battery core of lithium ion battery comprises the positive pole, inorganic electrolyte layer, polyelectrolyte floor and the negative pole that stack gradually.
Embodiment 3
The present embodiment is for illustration of high pressure lithium battery electric core disclosed by the invention and preparation method thereof.
The making of inorganic electrolyte layer:
By the inorganic electrolyte particle Li of 1000 grams
1.3al
0.3ti
1.7(PO
4)
3sinter at 900 DEG C, forming thickness is 250 μm of inorganic electrolyte layers.
The making of the first complex:
By 850 grams of positive electrode active materials LiMn
2o
4, 80 grams of Li
3pO
430 grams of bonding agent polyvinylidene fluoride, 20 grams of carbon nano-tube, 20g conductive agent HV join in 1800 grams of solvent NMP (1-METHYLPYRROLIDONE), then stir in de-airing mixer, form the anode sizing agent of stable uniform.This anode sizing agent is intermittently coated on inorganic electrolyte layer surface equably.Then 120 DEG C of oven dry, obtain positive electrode after roll squeezer compressing tablet.And then positive electrode surface-coated aluminium paste sintering, form plus plate current-collecting body.
The making of thin polymer film:
By the PVDF of 700 grams, the SiO of 300 grams
2join in the NMP of 1200 grams, then add thermal agitation and be modulated into slurry.This solution is coated on continuously on the inorganic electrolyte layer of aforementioned the first complex obtained, then 80 DEG C of oven dry, cut out and be of a size of 485 (length) × 46 (wide), the inorganic electrolyte layer of the first complex is formed the thin polymer film of 8 μm.
The making of negative pole:
940 grams of negative active core-shell material Delaniums, 40 grams of bonding agent polyvinyl alcohol and 40 grams of bonding agent SBR are joined in 1200 grams of deionized waters, then stirs in de-airing mixer, form the cathode size of stable uniform.This slurry is intermittently coated on Copper Foil equably, and (aluminium foil is of a size of: width 160 millimeters, thickness 16 microns) two sides on, then 120 DEG C of oven dry, after roll squeezer compressing tablet, cut out the negative pole for being of a size of 480 (length) × 45 (wide).
First complex alignment negative pole and surface with thin polymer film is placed in hot press, carries out 110 DEG C, 2MPa hot pressing 5 hours.
Sample after above-mentioned compacting is carried out fluid injection (now, thin polymer film absorption electrolyte, form polyelectrolyte floor), dry, pack, the step such as to change into, obtained lithium ion battery, wherein the battery core of lithium ion battery comprises the positive pole, inorganic electrolyte layer, polyelectrolyte floor and the negative pole that stack gradually.
Embodiment 4
The present embodiment is for illustration of high pressure lithium battery electric core disclosed by the invention and preparation method thereof.
The making of inorganic electrolyte layer:
By the inorganic electrolyte particle Li of 1000 grams
1.3al
0.3ti
1.7(PO
4)
3sinter at 1100 DEG C, forming thickness is 200 μm of inorganic electrolyte layers.
The making of the first complex:
By 850 grams of positive electrode active materials LiMn
2o
4, 80 grams of Li
3pO
430 grams of bonding agent polyvinylidene fluoride, 20 grams of carbon nano-tube, 20g conductive agent HV join in 1800 grams of solvent NMP (1-METHYLPYRROLIDONE), then stir in de-airing mixer, form the anode sizing agent of stable uniform.This anode sizing agent is intermittently coated on inorganic electrolyte layer surface equably.Then 120 DEG C of oven dry, obtain positive electrode after roll squeezer compressing tablet.And then positive electrode surface-coated aluminium paste sintering, form plus plate current-collecting body.
The making of negative pole:
940 grams of negative active core-shell material Delaniums, 40 grams of bonding agent polyvinyl alcohol and 40 grams of bonding agent SBR are joined in 1200 grams of deionized waters, then stirs in de-airing mixer, form the cathode size of stable uniform.This slurry is intermittently coated on Copper Foil equably, and (aluminium foil is of a size of: width 160 millimeters, thickness 16 microns) two sides on, then 120 DEG C of oven dry, after roll squeezer compressing tablet, cut out the negative pole for being of a size of 480 (length) × 45 (wide).
The making of the second complex:
By the PVDF of 800 grams, the TiO of 200 grams
2join in the NMP of 1500 grams, then add thermal agitation and be modulated into slurry.This slurry is coated on continuously on the aforementioned negative pole obtained, then 80 DEG C of oven dry, cuts out and be of a size of 485 (length) × 46 (wide), negative pole is formed the thin polymer film of 55 μm.
The alignment of the inorganic electrolyte layer of the thin polymer film of the second complex and the first complex is placed in hot press, carries out 110 DEG C, 2MPa hot pressing 5 hours.
Sample after above-mentioned compacting is carried out fluid injection (now, thin polymer film absorption electrolyte, form polyelectrolyte floor), dry, pack, the step such as to change into, obtained lithium ion battery, wherein the battery core of lithium ion battery comprises the positive pole, inorganic electrolyte layer, polyelectrolyte floor and the negative pole that stack gradually.
Embodiment 5
The present embodiment is for illustration of high pressure lithium battery electric core disclosed by the invention and preparation method thereof.
The making of positive pole:
By 880 grams of positive electrode active materials LiCoPO
4, 80 grams of LiNbO
3, 3 grams of bonding agent polyvinylidene fluoride, 5 grams of carbon blacks, 5g conductive agent HV join in 800 grams of solvent NMP (1-METHYLPYRROLIDONE), then stir in de-airing mixer, form the anode sizing agent of stable uniform.Intermittently be coated on the two sides of aluminium foil (aluminium foil is of a size of: width 160 millimeters, thickness 16 microns) equably by this anode sizing agent, then 120 DEG C of oven dry, obtain positive pole after roll squeezer compressing tablet.
The making of the first complex:
By the inorganic electrolyte particle Li of 950 grams
1.3al
0.3ti
1.7(PO
4)
3, the binding agent polyethylene glycol oxide of 5 grams joins in 1000 grams of deionized waters, then stir in de-airing mixer, form the inorganic electrolyte slurry of stable uniform.Be coated on continuously on aforementioned positive electrode by this slurry, then 45 DEG C of oven dry, obtain the first complex after roll squeezer compressing tablet.Wherein, inorganic electrolyte layer thickness is 120 μm.
The making of thin polymer film:
By the acrylic resin of 600 grams and the PS of 200 grams, the TiO of 200 grams
2join in the water of 1000 grams, be modulated into slurry.This slurry is coated on continuously on the inorganic electrolyte layer of aforementioned the first complex obtained, then 55 DEG C of oven dry, cut out and be of a size of 485 (length) × 46 (wide), the inorganic electrolyte layer of the first complex is formed the thin polymer film of 20 μm.
The making of negative pole:
940 grams of negative active core-shell material Delaniums, 5 grams of bonding agent polytetrafluoroethylene are joined in 1200 grams of deionized waters, then stirs in de-airing mixer, form the cathode size of stable uniform.This slurry is intermittently coated on Copper Foil equably, and (aluminium foil is of a size of: width 160 millimeters, thickness 16 microns) two sides on, then 120 DEG C of oven dry, after roll squeezer compressing tablet, cut out the negative pole for being of a size of 480 (length) × 45 (wide).
First complex alignment negative pole and surface with thin polymer film is placed in hot press, carries out 80 DEG C, 10MPa hot pressing 1 hour.
Sample after above-mentioned compacting is carried out fluid injection (now, thin polymer film absorption electrolyte, form polyelectrolyte floor), dry, pack, the step such as to change into, obtained lithium ion battery, wherein the battery core of lithium ion battery comprises the positive pole, inorganic electrolyte layer, polyelectrolyte floor and the negative pole that stack gradually.
Comparative example 1
This comparative example is used for comparative illustration high pressure lithium battery electric core disclosed by the invention and preparation method thereof.
Be the battery core that the polypropylene diaphragm of 20 μm is wound into rectangular lithium ion battery by positive pole identical for embodiment 1, negative pole and thickness, then through fluid injection, sealing, ageing, change into, namely obtain after partial volume the battery of this control experiment.
Comparative example 2
This comparative example is used 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 used 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
Following performance test is carried out to the above-mentioned battery prepared:
The battery each embodiment and comparative example prepared respectively gets 20, on LANDCT2001C secondary cell device for detecting performance, under 25 ± 1 DEG C of conditions, battery is carried out charge and discharge cycles test with 0.0.1C.Step is as follows: shelve 10min; Constant voltage charge ends to 5V/0.05C; Shelve 10min; Constant-current discharge, to 3.0V, is 1 circulation.Repeat this step, in cyclic process when battery capacity lower than discharge capacity first 80% time, loop termination, this cycle-index is the cycle life of battery, and often group is averaged.
Test result is as follows:
The circulating battery of embodiment 1 preparation 325 times;
The circulating battery of embodiment 2 preparation 316 times;
The circulating battery of embodiment 3 preparation 580 times;
The circulating battery of embodiment 4 preparation 632 times;
The circulating battery of embodiment 5 preparation 475 times;
Circulating battery prepared by comparative example 1 is less than 5 times, and percentage of batteries continues aerogenesis to battery swell in cyclic process, and then catches fire;
Be short-circuited in battery initial charge process prepared by comparative example 2, voltage keeps drops to zero, cannot circulate;
Circulating battery prepared by comparative example 3 is less than 10 times, and percentage of batteries continues aerogenesis to battery swell in cyclic process, and then catches fire.
Known by above-mentioned test, high pressure lithium battery electric core provided by the invention has excellent cycle performance and security performance, can effectively avoid electrolyte oxidized and the cycle performance of battery that causes and security performance decline.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (29)
1. a high pressure lithium battery electric core, is characterized in that, comprises positive pole, negative pole and the electrolyte between positive pole and negative pole;
Described electrolyte comprises inorganic electrolyte layer and is positioned at the polyelectrolyte floor on described inorganic electrolyte layer surface;
Described inorganic electrolyte layer is positioned at described positive electrode surface, and described polyelectrolyte floor is positioned at described negative terminal surface.
2. high pressure lithium battery electric core according to claim 1, is characterized in that, described inorganic electrolyte layer is the potsherd comprising NASICON type inorganic electrolyte and/or Ca-Ti ore type inorganic electrolyte.
3. high pressure lithium battery electric core according to claim 1, is characterized in that, described inorganic electrolyte layer comprises the first binding agent and inorganic electrolyte particle, and described inorganic electrolyte particle is NASICON type inorganic electrolyte and/or Ca-Ti ore type inorganic electrolyte.
4. the high pressure lithium battery electric core according to Claims 2 or 3, is characterized in that, described NASICON type inorganic electrolyte is LiM
2(PO
4)
3and one or more in alloy;
Wherein, M is selected from Ti, Zr, Ge, Sn or Pb;
Doped chemical in described alloy be selected from Mg, Ca, Sr, Ba, Sc, Al, Ga, In, Nb, Ta, V one or more;
Described Ca-Ti ore type inorganic electrolyte has following composition: A
xb
ytiO
3, A
xb
yta
2o
6, A
xb
ynb
2o
6, or A
hm
kd
nti
wo
3; Wherein x+3y=2, h+2k+5n+4w=6,0 < x < 2,0 < y < 2/3, h, k, n, w are all greater than 0; A be selected from Li, Na element one or more, B be selected from La, Ce, Pr, Y, Sc, Nd, Sm, Eu, Gd element one or more, M be selected from Sr, Ca, Ba, Ir, Pt element one or more, D be selected from Nb, Ta element one or more.
5. high pressure lithium battery electric core according to claim 3, it is characterized in that, described first binding agent is selected from polythiophene, polypyrrole, polytetrafluoroethylene, Kynoar, polyethylene, polypropylene, polystyrene, polyacrylamide, Ethylene-Propylene-Diene copolymer resins, styrene butadiene ribber, polybutadiene, fluorubber, Pluronic F-127, polyvinylpyrrolidone, mylar, acrylic resin, phenolic resins, epoxy resin, polyvinyl alcohol, carboxy-propyl cellulose, ethyl cellulose, polyethylene glycol oxide, sodium carboxymethylcellulose, one or more in styrene-butadiene latex.
6. high pressure lithium battery electric core according to claim 3, is characterized in that, in described inorganic electrolyte layer, with the weight of described inorganic electrolyte particle for benchmark, the content of described first binding agent is 0.5-20wt%.
7. according to the high pressure lithium battery electric core in claim 1-3,5,6 described in any one, it is characterized in that, described polyelectrolyte floor comprises gel polymer electrolyte or full solid state polymer electrolyte.
8. high pressure lithium battery electric core according to claim 7, is characterized in that, described gel polymer electrolyte comprises thin polymer film and is adsorbed in the electrolyte in described thin polymer film.
9. high pressure lithium battery electric core according to claim 8, is characterized in that, described polyelectrolyte floor also comprises inorganic nanoparticles; Described inorganic nanoparticles is selected from nano level TiO
2, SiO
2, Al
2o
3, ZrO
2in one or more; In described polyelectrolyte floor, with the weight of described thin polymer film for benchmark, the content of described inorganic nanoparticles is 0.5-90wt%.
10. according to the high pressure lithium battery electric core in claim 1-3,5,8,9 described in any one, it is characterized in that, the thickness of described inorganic electrolyte layer is 50-600 μm, and the thickness of described polyelectrolyte floor is 2-100 μm.
11., according to the high pressure lithium battery electric core in claim 1-3,5,8,9 described in any one, is characterized in that, described positive pole comprises plus plate current-collecting body and is positioned at the positive electrode on plus plate current-collecting body;
Described positive electrode comprises positive active material; Described positive active material is selected from LiNi
0.5mn
1.5o
4, LiMn
2o
4, LiCoPO
4, LiNiPO
4, Li
3v
3(PO
4)
3in one or more.
12. high pressure lithium battery electric cores according to claim 11, is characterized in that, also comprise solid electrolyte additive in described positive electrode, described solid electrolyte additive is selected from LiNbO
3, LiTaO
3, Li
x1la
1/ (3-x1) TaO
3, Li
3pO
4, Li
x2ti
y2(PO
4)
3, Li
x3al
y3ti
z3(PO
4)
3, Li
2siO
3, Li
2o, Li
2s, Li
2s-P
2s
5, Li
2s-SiS
2-P
2s
5, Li
x4si
y4s
z4, Li
x5p
y5s
z5, LiBO
2, Li
3.6si
0.6p
0.4o
4in one or more, wherein, 0 < x
1< 3; 0 < x
2< 2,0 < y
2< 3; 0 < x
3< 2,0 < y
3< 1,0 < z
3< 3; 0 < x
4< 3,0 < y
4< 2,0 < z
4< 4; 0 < x
5< 3,0 < y
5< 3,0 < z
5< 7.
13. high pressure lithium battery electric cores according to claim 11, is characterized in that, described positive electrode, and with the weight of positive active material for benchmark, the content of described solid electrolyte additive is 0.1-50wt%.
The preparation method of 14. high pressure lithium battery electric cores as claimed in claim 1, is characterized in that, the positive pole, inorganic electrolyte layer, thin polymer film, the negative pole that comprise stacking gradually are compressing, then in thin polymer film, adsorb electrolyte; Form the high pressure lithium battery electric core comprising positive pole, inorganic electrolyte layer, polyelectrolyte floor and negative pole.
15. preparation methods according to claim 14, is characterized in that, described compressing before also comprise formation first complex, described first complex comprises positive pole and is positioned at the inorganic electrolyte layer of positive electrode surface.
16. preparation methods according to claim 15, is characterized in that, the method for described formation first complex comprises: provide positive pole, and described positive pole comprises plus plate current-collecting body and is positioned at the positive electrode of anode collection surface; Then at the described inorganic electrolyte layer of described positive electrode surface preparation.
17. preparation methods according to claim 16, it is characterized in that, comprise in the method for the described inorganic electrolyte layer of described positive electrode surface preparation: at described positive electrode surface-coated inorganic electrolyte slurry, then dry at 50-200 DEG C, carry out compressing tablet again, form described inorganic electrolyte layer on described positive electrode surface;
Described inorganic electrolyte slurry comprises the first binding agent, inorganic electrolyte particle and the first solvent; With the weight of described inorganic electrolyte particle for benchmark, the content of described first binding agent is 0.5-20wt%, and the content of described first solvent is 20-350wt%;
Described inorganic electrolyte particle is NASICON type inorganic electrolyte and/or Ca-Ti ore type inorganic electrolyte; Described NASICON type inorganic electrolyte is LiM
2(PO
4)
3and one or more in alloy;
Wherein, M is selected from Ti, Zr, Ge, Sn or Pb;
Doped chemical in described alloy be selected from Mg, Ca, Sr, Ba, Sc, Al, Ga, In, Nb, Ta, V one or more;
Described Ca-Ti ore type inorganic electrolyte has following composition: A
xb
ytiO
3, A
xb
yta
2o
6, A
xb
ynb
2o
6, or A
hm
kd
nti
wo
3; Wherein x+3y=2, h+2k+5n+4w=6,0 < x < 2,0 < y < 2/3, h, k, n, w are all greater than 0; A be selected from Li, Na element one or more, B be selected from La, Ce, Pr, Y, Sc, Nd, Sm, Eu, Gd element one or more, M be selected from Sr, Ca, Ba, Ir, Pt element one or more, D be selected from Nb, Ta element one or more;
Described first binding agent is selected from polythiophene, polypyrrole, polytetrafluoroethylene, Kynoar, polyethylene, polypropylene, polystyrene, polyacrylamide, Ethylene-Propylene-Diene copolymer resins, styrene butadiene ribber, polybutadiene, fluorubber, Pluronic F-127, polyvinylpyrrolidone, mylar, acrylic resin, phenolic resins, epoxy resin, polyvinyl alcohol, carboxy-propyl cellulose, ethyl cellulose, polyethylene glycol oxide, sodium carboxymethylcellulose, one or more in styrene-butadiene latex,
Described first solvent be selected from water, acetone, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), DMF, ethanol one or more.
18. preparation methods according to claim 15, it is characterized in that, the method of described formation first complex comprises: provide inorganic electrolyte layer, and described inorganic electrolyte layer is the potsherd comprising NASICON type inorganic electrolyte and/or Ca-Ti ore type inorganic electrolyte; Then form positive electrode on described inorganic electrolyte layer surface, then form plus plate current-collecting body on described positive electrode.
19. preparation methods according to claim 18, is characterized in that, are sintered by inorganic electrolyte particle at 800-1200 DEG C, form described inorganic electrolyte layer;
Described inorganic electrolyte particle is NASICON type inorganic electrolyte and/or Ca-Ti ore type inorganic electrolyte; Described NASICON type inorganic electrolyte is LiM
2(PO
4)
3and one or more in alloy;
Wherein, M is selected from Ti, Zr, Ge, Sn or Pb;
Doped chemical in described alloy be selected from Mg, Ca, Sr, Ba, Sc, Al, Ga, In, Nb, Ta, V one or more;
Described Ca-Ti ore type inorganic electrolyte has following composition: A
xb
ytiO
3, A
xb
yta
2o
6, A
xb
ynb
2o
6, or A
hm
kd
nti
wo
3; Wherein x+3y=2, h+2k+5n+4w=6,0 < x < 2,0 < y < 2/3, h, k, n, w are all greater than 0; A be selected from Li, Na element one or more, B be selected from La, Ce, Pr, Y, Sc, Nd, Sm, Eu, Gd element one or more, M be selected from Sr, Ca, Ba, Ir, Pt element one or more, D be selected from Nb, Ta element one or more.
20. preparation methods according to claim 18, is characterized in that, describedly form the method for positive electrode on inorganic electrolyte layer surface and comprise: at inorganic electrolyte layer surface-coated anode sizing agent, and compressing tablet, oven dry;
The method of described formation plus plate current-collecting body is vapour deposition or applies plus plate current-collecting body slurry and sinter.
21., according to the preparation method in claim 15-20 described in any one, is characterized in that, the inorganic electrolyte layer surface being included in described first complex forms described thin polymer film, is then placed on described thin polymer film by negative pole compressing.
22. preparation methods according to claim 21, is characterized in that, the method forming described thin polymer film on inorganic electrolyte layer surface is: at described inorganic electrolyte layer surface-coated polymer paste, then dry;
Described polymer paste comprises polymer and the second solvent, and with described polymer weight for benchmark, the content of described second solvent is 30-2000wt%;
Described polymer is selected from one or more in Kynoar, Kynoar-hexafluoropropylene, polyacrylonitrile, polytetrafluoroethylene, polymethyl methacrylate, polyethyl methacrylate, the two maleic mono-ester of polyethylene glycol, polystyrene, polyoxyethylene, polyimides, acrylic resin, epoxy resin; Described second solvent be selected from 1-METHYLPYRROLIDONE, water, acetone, dimethyl sulfoxide (DMSO), DMF, ethanol, oxolane one or more.
23. preparation methods according to claim 22, is characterized in that, described polymer paste also comprises inorganic nanoparticles; Described inorganic nanoparticles is selected from nano level TiO
2, SiO
2, Al
2o
3, ZrO
2in one or more;
With described polymer weight for benchmark, the content of described inorganic nanoparticles is 0.5-90wt%.
24., according to the preparation method in claim 15-20 described in any one, is characterized in that, comprise and provide negative pole, and described negative pole comprises negative current collector and is positioned at the negative material of described negative pole currect collecting surface;
Then form described thin polymer film on described negative material surface, obtain second complex with stacked negative pole and thin polymer film;
Again by the first complex and the second complex stacked, inorganic electrolyte layer is contacted with thin polymer film, then compressing.
25. preparation methods according to claim 24, is characterized in that, the method forming described thin polymer film on negative material surface is: at described negative material surface-coated polymer paste, then dry;
Described polymer paste comprises polymer and the second solvent, and with described polymer weight for benchmark, the content of described second solvent is 30-2000wt%;
Described polymer is selected from one or more in Kynoar, Kynoar-hexafluoropropylene, polyacrylonitrile, polytetrafluoroethylene, polymethyl methacrylate, polyethyl methacrylate, the two maleic mono-ester of polyethylene glycol, polystyrene, polyoxyethylene, polyimides, acrylic resin, epoxy resin; Described second solvent be selected from 1-METHYLPYRROLIDONE, water, acetone, dimethyl sulfoxide (DMSO), DMF, ethanol, oxolane one or more.
26. preparation methods according to claim 25, is characterized in that, described polymer paste also comprises inorganic nanoparticles; Described inorganic nanoparticles is selected from nano level TiO
2, SiO
2, Al
2o
3, ZrO
2in one or more;
With described polymer weight for benchmark, the content of described inorganic nanoparticles is 0.5-90wt%.
27. according to the preparation method in claim 14-20,22,23,25,26 described in any one, and it is characterized in that, described compressing method is: at 50-300 DEG C, hot pressing 0.05-10h under 0.1-50MPa.
28., according to the preparation method in claim 14-20,22,23,25,26 described in any one, is characterized in that, the thickness of described inorganic electrolyte layer is 50-600 μm, and the thickness of described thin polymer film is 2-100 μm.
29. 1 kinds of lithium ion batteries, is characterized in that, comprise housing and be positioned at the battery core of described housing, described battery core is the high pressure lithium battery electric core in claim 1-13 described in any one.
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