CN1142613C - Secondary Li ion battery using colloidal polymer as electrolyte and its preparing process - Google Patents
Secondary Li ion battery using colloidal polymer as electrolyte and its preparing process Download PDFInfo
- Publication number
- CN1142613C CN1142613C CNB001055410A CN00105541A CN1142613C CN 1142613 C CN1142613 C CN 1142613C CN B001055410 A CNB001055410 A CN B001055410A CN 00105541 A CN00105541 A CN 00105541A CN 1142613 C CN1142613 C CN 1142613C
- Authority
- CN
- China
- Prior art keywords
- anode
- electrolyte
- coated
- negative electrode
- pole piece
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention belongs to the technical field of the manufacture of secondary lithium ion batteries. A secondary lithium ion battery of the present invention is composed of a positive electrode using carbon as an active material, a negative electrode using transition metal oxide containing lithium as an active material, a colloid polymer electrolyte, a polymer membrane, etc. The present invention uses a colloid polymer as an electrolyte and has the advantages of high safety, high stability, simple manufacturing process, high energy density, low manufacturing cost and high periodicity; the present invention is suitable for charging and discharging heavy current, and the manufacture of thin batteries in various shapes, etc. The secondary lithium ion battery of the present invention is suitable for the fields of mobile telephones, notebook computers, portable cameras, CD displayers, electronic toys, electric vehicles, etc.
Description
Technical field
The invention belongs to the high-energy battery technical field, particularly make the technical field of slim room temperature after polymerization thing lithium ion battery.
Technical background
Fast development along with the electronic technology and the communication technology, the volume of portable type electronic product that with the present mobile communication terminal is representative is more and more littler, thereby portable power source has been proposed requirements at the higher level, and to the energy density height, the demand of the thin lithium ion battery that volume is little is also more urgent.
Diaphragm material in the thin lithium ion battery and state between the electrolyte and electrode structure are different from the multi-lay winding structure in the cylindrical battery.The quality of lithium ion battery performance, except that the chemical property of electrode material, electrode structure, battery structure and battery design also are the key factors of its performance of decision.Under certain condition, good structure can make battery performance greatly improve.Electrode structure in the thin lithium ion battery belongs to larger area plane multilayer folding structure, the sealing of employing flexible packing material, electrode combines not tight with barrier film, be unfavorable for the conduction of lithium ion, thereby reduce the energy density and the efficiency for charge-discharge of battery, so thin lithium ion battery to the integrality of interface combination requirements at the higher level has been proposed.Bonding for guaranteeing good interface, must abandon traditional liquid electrolyte and adopt the strong polymer electrolyte of plasticity, so polymer Li-ion battery becomes the first-selection of thin lithium ion battery.At present, the research of relevant various forms of solid polymer electrolytes concentrates on following several respects: the polymeric system that adds lithium salts after the polyblend of (1) two or more opposed polarities again; (2) micromolecule adds lithium salts polymerization and crosslinked polymeric system again: the earlier crosslinked back polymerization of (3) micromolecule adds the polymeric system of lithium salts again; (4) big molecule adds the crosslinked again polymeric system of lithium salts and relevant interpenetrating polymer networks system (referring to document 1, plant Gu Qingxiong, ア Network リ Le is copolymer ボ リ マ one a ゲ Le electrolyte, industrial materials, Vol.47, No.2,48 (1999); Document 2, rock are just abundant for a long time, Koyama Sheng, and PAN system, PMMA are ボ リ マ one ゲ Le electrolyte, industrial materials, Vol.47, No.2,62 (1999); Document 3, D.W.Kim and Y.K.Sun.Polymer Electrolyte Based on Acrylonitrile MethylMethacrylate Styrene Terpolymers for Rechargeable Lithium PolymerBatteries.J.Electrochem.Soc, Vol.145, No.6,1958 (1998); Document 4, K.Z.ghib andM.Armand, Electrochemistry of Anodes in Solid State Li-Ion PolymerBatteries.J.Electrochem.Soc., Vol.145,3135 (1998); Document 5, T.Sato, BatteryHaving Solid Ion Conductive Polymer Electrolyte.U.S.Patent.5641590; Document 6, M.Matsumoto, Solid Polymer Electrolyte and Method of ManufactureThereof.U.S.Patent.5585039).Because of various technical reasons, lead the more high and industrialization of being unrealized of lower, bad mechanical strength, complicated process of preparation and cost as electricity.
Summary of the invention
The objective of the invention is to improve the deficiency of prior art, providing a kind of is electrolytical secondary lithium battery and preparation method thereof with colloidal polymer.The present invention is an electrolyte with the colloidal polymer than liquid electrolyte safety that is used for thin lithium ion battery, this preparation of electrolyte technology is simple, can be directly be assembled into thin lithium ion battery with the positive/negative plate that is used to make liquid cell, make the pole piece coating device of liquid cell can form tinuous production with the electrolytical synthesizer of colloidal polymer, thereby greatly save equipment investment without just transforming.
The object of the present invention is achieved like this:
Of the present inventionly be used to prepare electrolytical each component material of colloidal polymer and comprise:
(1) polymerization single polymerization monomer: the acrylic ester monomer that can carry out radical polymerization or ionic polymerization, as methyl methacrylate, EMA, propyl methacrylate, isobutyl methacrylate, butyl methacrylate, EHMA, allyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, alkoxyl (contracting) diethylene glycol monoacrylate, (contracting) glycol diacrylate, alkoxyl (contracting) ethylene glycol methacrylate, (contracting) ethylene glycol dimethacrylate.
(2) electrolyte: the mixed solvent that one or more organic solvents are formed adds one or more solubility lithium salts and forms electrolyte, organic solvent comprises vinyl carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl-methyl carbonic ester (ENC), dimethoxy-ethane (DME); Typical solubility lithium salts comprises LiN (CF
3SO
2)
3, LiClO
4, LiBF
4, LiPF
6, LiC
3SO
3, LiN (CF
3SO
2)
2, LiAsF
6Typical system comprises 1M LiPF
6(EC/DEC volume ratio 1: 1), 1M LiPF
6(EC/DMC volume ratio 3: 7).
(3) initator: can adopt thermal initiator or light trigger.Thermal initiator comprises a kind of in the following initator at least: (1) azo-initiator: mainly be azobisisobutyronitrile, and azo two eyeball in different heptan; (2) peroxide initator: dialkyl peroxide mainly is a di-tert-butyl peroxide, cumyl peroxide; Peroxidating two acyls mainly are dibenzoyl peroxides, dilauroyl peroxide; Organic hydroperoxide mainly is an isopropyl benzene hydroperoxide; Peroxy dicarbonate mainly is a di-isopropyl peroxydicarbonate, di-cyclohexylperoxy di-carbonate; (3) redox initiation system: as the tertiary amine that comprises of reducing agent, mainly be N, accelerine; Naphthenate; Organo-metallic compound mainly is a diethyl zinc; Boron triethyl; Typical redox initiation system comprises dibenzoyl peroxide and N, the initiator system that accelerine is formed.Light trigger comprises a kind of in the following initator at least: (1) styrax ethers initator mainly is a benzoin isobutyl butyl ether, benzoin isobutyl propyl group ether, benzoin methyl ether, benzoin ethyl ether; (2) ketone and derivative thereof or ketone-amine system initator mainly is a benzophenone, 4,4 '-(N, TMSDMA N dimethylamine base) benzophenone, acetophenone, diethoxy acetophenone, isopropyl thioxanthone, 2-methyl thioxanthone, xanthone; (3) benzil and acetals initator; (4) fused ring compound derivatives class initator extremely mainly is naphthalene and acetonaphthone, quinones, anthracene class, pyrene; (5) the monoxime ester class initator of alkyl-phenyl ketone mainly is a diacetyl monoxime ester, benzil monoxime ester; (6) azo-initiator.
(4) nanophase powder: as nano silicon, nano aluminium oxide.
(5) membrane for polymer: porous polypropylene (PP) film, porous polyethylene membrane and composite membrane thereof that (1) is general, as Celgard2300,2400 etc., (2) porous Kynoar (PVDF) the paraphase film or the noninvert film of various technologies (wet method and dry method etc.) preparation comprise the barrier film that adds organic and inorganic powder; Add the barrier film of organic and inorganic short fiber; With the barrier film of other one or more polyblends, (3) porous polypropylene eyeball (PAN) film, porous polyoxyethylene (PEO) film that (4) fiber or powder strengthen.
Of the present invention is that electrolytical preparation is to adopt following step to realize with colloidal polymer:
(1), divides anhydrate branch and other impurity with the polymerization single polymerization monomer rectification and purification;
(2) (vacuum degree-0.1Mpa) moisture was removed in oven dry in 12-24 hour in 5-30 ℃ vacuum drying oven with initator and membrane for polymer;
(3) mentioned component being moved into together water content is lower than in the inert atmosphere glove box of 1.0ppm;
(4) by electrolyte and polymerization single polymerization monomer volume ratio 15: 1-1: 1, the weight ratio 10 of polymerization single polymerization monomer and initator: 1-100: 1, the nanophase inorganic powder proportioning that accounts for polymerization single polymerization monomer weight 10%-70% is mixed into homogeneous phase solution with electrolyte, polymerization single polymerization monomer, initator, nanophase inorganic powder in the glass container of cleaning;
(5) membrane for polymer is immersed above-mentioned mixed solution;
(6) above-mentioned system sealing back is taken out from glove box, and place 0 ℃-100 ℃ baking oven polymerase 10 .1 hour-15 hours, forms colloidal fluid water white, that have certain viscosity and flowability.
Can also not add the nanophase powder in the reaction system.
Can also not add initator in the reaction system, but extend to 24 hours heating time.
Electrolyte, monomer, initator can also be mixed in the quartz container of cleaning, immerse barrier film and the taking-up of sealing back, at power is the uviol lamp (ultraviolet light dominant wavelength is distributed in 300-360nm) irradiation 0.1-1 hour down of 300-500W, forms water white transparency, has certain viscosity and mobile colloidal fluid; In reaction system, initator can also do not added but exposure time extends to 2 hours; In reaction system, can also add behind the nanophase powder that accounts for polymerization single polymerization monomer weight 10%-70% initiated polymerization again.
The reaction system that adds or do not add the sealing of initator can also adopt the initiation mode initiated polymerization of gamma-ray irradiation or electron beam irradiation to prepare the colloidal polymer electrolyte, and exposure time 0.01-1 hour, irradiation intensity 10-100Gy; In reaction system, can also add behind the nanophase powder that accounts for polymerization single polymerization monomer weight 10%-70% initiated polymerization again.
Barrier film is immersed 1-10 hour again after mixed solution can also being aggregated into colloidal electrolyte earlier.
The active material of cathode of secondary lithium battery of the present invention is for reversibly embedding or deviate from the lithium-containing transition metal oxide of lithium, as LiCoO
2, LiNiO
2, LiMn
2O
4Deng.The preparation method of negative electrode pole piece is as follows: with active material of cathode, conductive additive powder (granularity 1-1000nm, as acetylene black, carbon black, graphite powder, various oxides, sulfide, halide powder), bonding agent (as-Ding dimethyl formamide (DMF) solution of vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HPF Copolymer) of concentration) etc. mixing, make the composite mortar of homogeneous at normal temperatures and pressures, slurry evenly is coated on the aluminium foil (thickness 15-20um) as collector, then 100-160 ℃ of oven dry down, the gained film thickness is at 50-100um, densification continues to dry by the fire 12 hours down at 100-160 ℃ then.In the pole piece after the oven dry, cathode active material accounts for the 85wt% that always is coated with application, copolymer comprised 5wt%, and dispersant accounts for 10wt%.Both cathode material can be coated in the single face of aluminium foil, also can be coated in the two-sided of aluminium foil, and then the gained pole piece had been cut into required form by the battery specification for preparing and be negative electrode.
The active material of positive electrode that contains the electrolytical secondary lithium battery of colloidal polymer of the present invention is various material with carbon elements, comprises soft carbon, hard carbon etc., as MCMB (granularity 15um).The preparation method of anode is as follows: the compound slurry that material with carbon element and bonding agent (as dimethyl formamide (DMF) solution of certain density Kynoar (PVDF)) is mixed and made into homogeneous, evenly be coated on the collector then, collector is on the paper tinsel, net porous body, foams, corpus fibrosum of various conductions, as carriers such as Copper Foil, nickel screen, nickel foam, carbon felts, mainly be to be coated on the Copper Foil (thickness 10-15um).Gained film thickness 40-90um, 100-160 ℃ of oven dry down, densification continues to dry by the fire 12 hours down at 100-160 ℃ then.In the pole piece after the oven dry, anode active material accounts for the 94wt% that always is coated with application, and bonding agent accounts for 6wt%.Both anode material can be coated in the single face of Copper Foil, also can be coated in the two-sided of Copper Foil, and then the gained pole piece had been cut into required form by the battery specification for preparing and be anode.
Of the present invention is that the basic structure of electrolytical secondary lithium battery is by being the anode of active material with the material with carbon element with colloidal polymer, with the transition metal oxide that contains lithium is the negative electrode of active material, the colloidal polymer electrolyte, membrane for polymer, the composite film packaging bag, lead-in wire, fluid sealant is formed.Bonding and separate anode and negative electrode (both can also can not flooding with the electrolyte dipping in advance) in glove box with fully flooding the electrolytical barrier film of colloidal polymer, draw two lead-in wires respectively from the same end of negative electrode and anode.It is bonding that negative electrode and anode both can individual layers, bonding after also can multilayer folding, in the packaging bag that the aluminium/polyethylene composite film of packing into is then made, draws two lead-in wires from openend, vacuumizes the back hot sealing.
Secondary lithium battery of the present invention can be made button (individual layer), column type (multilaminate coiled), square specifications such as (multilayer foldings).
Of the present invention is that electrolytical secondary lithium battery has good chemistry and electrochemical stability with colloidal polymer.The colloidal polymer electrolyte has certain viscosity and flowability, its ionic conductivity is than total solids polymer dielectric height, help the migration of lithium ion, and can be filled in the space of the micropore of barrier film and barrier film and electrode interface, make that barrier film and electrode are complete to be contacted, improve the compactness of adhering at interface, thereby reduced the interface impedance and the internal resistance of cell of electrolyte and electrode, helped large current density.
The present invention is owing to use the colloidal polymer electrolyte to substitute liquid electrolyte, has that fail safe is good, manufacturing process is simple, energy density is high, cyclicity is good, is suitable for advantage such as large current density, is particularly suitable for making the thin battery of different shape.Of the present invention is that electrolytical secondary lithium battery is applicable to multiple occasion with colloidal polymer, need the occasion of portable power source as mobile phone, beep-pager, notebook computer, palmtop PC, field camera and CD player, electronic toy, electric tool etc., also applicable to fields such as electric automobiles.
Description of drawings
Fig. 1 is the structural representation of button Experimental cell among the present invention,
Fig. 2 is the structural representation of slim multilayer folding Experimental cell among the present invention,
Fig. 3 is the charging and discharging curve in the 1st and the 10th week of the embodiment of the invention 1 Experimental cell,
Fig. 4 is the charging and discharging curve in the 1st and the 10th week of the embodiment of the invention 2 Experimental cells,
Fig. 5 is the charging and discharging curve in the 1st and the 10th week of the embodiment of the invention 3 Experimental cells,
Fig. 6 is the charging and discharging curve in the 1st and the 10th week of the embodiment of the invention 4 Experimental cells,
Fig. 7 is the charging and discharging curve in the 1st and the 10th week of the embodiment of the invention 5 Experimental cells,
Fig. 8 is the charging and discharging curve in the 1st and the 10th week of the embodiment of the invention 6 Experimental cells,
Fig. 9 is the charging and discharging curve in the 1st and the 10th week of the embodiment of the invention 7 Experimental cells,
Figure 10 is the charging and discharging curve in the 1st and the 10th week of the embodiment of the invention 8 Experimental cells,
Drawing is described as follows: first week of 1 expression charging and discharging curve, 2 stainless steel sealing nuts (being connected with negative electrode), 3 polytetrafluoroethylene nuts, 4 stainless steel steel columns, 5 polytetrafluoroethyllining lining, 6 stainless steel cylinders (being connected) with anode, 7 aluminium foils, 8 active material of cathode, the electrolytical barrier film of 9 dipping colloidal polymers, the tenth week of 10 expression charging and discharging curves, 11 active material of positive electrode, 12 Copper Foils, 13 cathode legs, 14 anode taps, 15 aluminium/polyethylene composite film packaging bag
The cyclicity parameter is that the difference of the tenth all discharge capacities and first all discharge capacities is divided by the discharge capacity first time in the table 1; The reversible capacity value is based on active material of positive electrode, and promptly the tenth all discharge capacities are divided by the active material of positive electrode quality; First all efficient is meant that first all discharge capacities are divided by first all charging capacitys; Second all efficient is meant that second all discharge capacities are divided by second all charging capacitys.
Embodiment
[embodiment 1]
Adopt Experimental cell to study the chemical property that contains the electrolytical secondary lithium battery of colloidal polymer of the present invention.In being lower than the argon gas glove box of 1.0ppm, water content assembles Experimental cell by battery structure shown in the accompanying drawing 1.Polymerization single polymerization monomer adopts the methyl methacrylate (MMA) of rectification and purification, and initator adopts the pure azobisisobutyronitrile of dewatered analysis (AIBN), and electrolyte adopts 1MLiPF
6(EC/DEC volume ratio 1: 1), barrier film adopt Celgard2300 type porous polypropylene barrier film.
100: 1 proportioning of weight ratio by electrolyte and MMA volume ratio 10: 1, MMA and AIBN is mixed into homogeneous phase solution with electrolyte, MMA, AIBN in the glass container of cleaning, it is 1.8cm that barrier film is cut into area
2Disk and be dipped in the solution, 70 ℃ baking oven polymerization 12 hours is taken out and placed in sealing back from glove box, form water white transparency, have certain viscosity and mobile colloidal fluid, moves in the glove box again.
With LiCoO
2Dimethyl formamide (DMF) solution of powder, carbon black (granularity 1000nm), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HPF Copolymer) mixes, make the composite mortar of homogeneous at normal temperatures and pressures, slurry evenly is coated on the aluminium foil (thickness 15-20um) as collector, then 160 ℃ of oven dry down, the gained film thickness is at 50-100um, densification continues to dry by the fire 12 hours down at 160 ℃ then.In the pole piece after the oven dry, LiCoO
2Account for the 85wt% that always is coated with application, copolymer comprised 5wt%, carbon black accounts for 10wt%.The gained pole piece being cut into area then is 1cm
2Disk as negative electrode.
MCMB (granularity 15um) is become the composite mortar of homogeneous with dimethyl formamide (DMF) solution mixing system of Kynoar (PVDF), evenly be coated in then on the Copper Foil (thickness 10-15um) as collector.Gained film thickness 40-90um, 160 ℃ of oven dry down, densification continues to dry by the fire 12 hours down at 160 ℃ then.In the pole piece after the oven dry, MCMB accounts for the 94wt% that always is coated with application, and Kynoar (PVDF) accounts for 6wt%.The gained pole piece being cut into area then is 1cm
2Disk as anode.
Dried pole piece is moved in the argon gas glove box, from synthetic colloidal polymer electrolyte, take out barrier film, pole piece is bonded together, shown in accompanying drawing 1, be assembled into Experimental cell.LiCoO in the battery of assembling on cathode sheets and the anode strip
2With the weight ratio of MCMB be 2.4-2.5: 1.
Experimental cell carries out the charge and discharge cycles test on micro-processor controlled auto charge and discharge instrument.Current density 0.2mA/cm
2, charging cut-ff voltage 42V, discharge cut-off voltage 2.5V.Discharge and recharge data and list in the subordinate list 1, Experimental cell is seen accompanying drawing 3 at the charging and discharging curve in first week and the tenth week.[embodiment 2]
Negative electrode, anode, the electrolytical preparation process of colloidal polymer are with embodiment one, the negative electrode and the anode pole piece that cut soak with electrolyte in advance, and then bonding and separate with dipping colloidal polymer electrolytical barrier film pole piece, the assembling of all the other Experimental cells and method of testing are with embodiment one.
Discharge and recharge data and list in the subordinate list 1, Experimental cell is seen accompanying drawing 4 at the charging and discharging curve in first week and the tenth week.[embodiment 3]
Negative electrode, anode, the electrolytical preparation process of colloidal polymer be with embodiment one, and it is 4cm that dried negative electrode and anode are cut into area
2(pole piece of 2cm * 2cm) also soaks with electrolyte in advance, and then (2.2cm * 2.2cm) is bonding and separate pole piece, is assembled into Experimental cell shown in accompanying drawing 2 with flooding the electrolytical barrier film of colloidal polymer.LiCoO in the battery of assembling on cathode sheets and the anode strip
2With the weight ratio of MCMB be 2.4-2.5: 1.The Experimental cell clamp is carried out the charge and discharge cycles test, first all current density 0.05mA/cm on micro-processor controlled auto charge and discharge instrument
2, charging cut-ff voltage 4.3V, discharge cut-off voltage 2.7V; Current density 0.75mA/cm after second week
2, charging cut-ff voltage 4.2V, discharge cut-off voltage 2.7V.
Discharge and recharge data and list in the subordinate list 1, Experimental cell is seen accompanying drawing 5 at the charging and discharging curve in first week and the tenth week.[embodiment 4]
With LiCoO
2Dimethyl formamide (DMF) solution of powder, carbon black (granularity 1000nm), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HPF Copolymer) mixes, make the composite mortar of homogeneous at normal temperatures and pressures, with slurry equably double-coated on aluminium foil (thickness 15-20um) as collector.Other condition and preparation process are with embodiment one.
MCMB (granularity 15um) is become the composite mortar of homogeneous with dimethyl formamide (DMF) solution mixing system of the Kynoar (PVDF) of wt%, then equably double-coated on Copper Foil (thickness 10-15um) as collector.Other condition and preparation process are with embodiment one.
The electrolytical preparation process of colloidal polymer is with embodiment one, and it is 17.5cm that dried negative electrode and anode are cut into area
2(pole piece of 5.0cm * 3.5cm) also soaks with electrolyte in advance, and then (5.5cm * 4.0cm) is bonding and separate pole piece, is assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2 with flooding the electrolytical barrier film of colloidal polymer.LiCoO in the battery of assembling on cathode sheets and the anode strip
2With the weight ratio of MCMB be 2.4-2.5: 1.The Experimental cell clamp is carried out the charge and discharge cycles test, first all current density 0.2mA/cm on micro-processor controlled auto charge and discharge instrument
2, charging cut-ff voltage 4.3V, discharge cut-off voltage 2.7V; Current density 0.6mA/cm after second week
2, charging cut-ff voltage 42V, discharge cut-off voltage 2.7V.
Discharge and recharge data and list in the subordinate list 1, Experimental cell is seen accompanying drawing 6 at the charging and discharging curve in first week and the tenth week.[embodiment 5]
100: 1 proportioning of weight ratio by electrolyte and MMA volume ratio 10: 1, MMA and AIBN is mixed into homogeneous phase solution with electrolyte, MMA, AIBN in the glass container of cleaning, 70 ℃ baking oven polymerization 12 hours is taken out and placed in sealing back from glove box, form water white transparency, have certain viscosity and mobile colloidal fluid, move in the glove box again.(5.5cm * 4.0cm) immerses in the colloidal polymer electrolyte and takes out after 5 hours, and is bonding and separate pole piece, is assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2 with the barrier film that cuts.The preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.
Discharge and recharge data and list in the subordinate list 1, Experimental cell is seen accompanying drawing 7 at the charging and discharging curve in first week and the tenth week.[embodiment 6]
By electrolyte and 10: 1 proportioning of MMA volume ratio electrolyte, MMA are mixed into solution in the glass container of cleaning, 80 ℃ baking oven polymerization 24 hours is taken out and placed in sealing back from glove box, form water white transparency, have certain viscosity and mobile colloidal fluid, move in the glove box again.(5.5cm * 4.0cm) immerses in the colloidal polymer electrolyte and takes out after 5 hours, and is bonding and separate pole piece, is assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2 with the barrier film that cuts.The preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.
Discharge and recharge data and list in the subordinate list 1, Experimental cell is seen accompanying drawing 8 at the charging and discharging curve in first week and the tenth week.[embodiment 7]
By electrolyte and 10: 1 proportioning of MMA volume ratio electrolyte, MMA are mixed into solution in the glass container of cleaning, with the barrier film (5.5cm * 4.0cm) be dipped in the solution that cuts, 80 ℃ baking oven polymerization 24 hours is taken out and placed in sealing back from glove box, form water white transparency, have certain viscosity and mobile colloidal fluid, move into glove box again.Take out barrier film with negative electrode and anodically-bonded and separate from the colloidal polymer electrolyte, be assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2, the preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.
Discharge and recharge data and list in the subordinate list 1, Experimental cell is seen accompanying drawing 9 at the charging and discharging curve in first week and the tenth week.[embodiment 8]
The preparation condition of negative electrode, anode is with embodiment four.
100: 1 proportioning of weight ratio by electrolyte and MMA volume ratio 10: 1, MMA and AIBN is mixed into homogeneous phase solution with electrolyte, MMA, AIBN in the glass container of cleaning.With the area that cuts is that (barrier film of 5.5cm * 4.0cm) separates negative electrode and anode to 22cm2, be assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2, before the packaging bag sealing, mixed solution is injected packaging bag, the barrier film and the pole piece that fold are fully soaked, then with the packaging bag sealed after being vacuumized, from glove box, take out and place 70 ℃ baking oven polymerization 12 hours, make the multilayer folding Experimental cell.The test condition of battery is with embodiment four.
Discharge and recharge data and list in the subordinate list 1, Experimental cell is seen accompanying drawing 10 at the charging and discharging curve in first week and the tenth week.[embodiment 9]
Pressed electrolyte and MMA volume ratio 10: 1,50: 1 the proportioning of weight ratio of MMA and light trigger benzophenone (BP) is with electrolyte, MMA, BP is mixed into homogeneous phase solution in the quartz container of cleaning, with the barrier film (5.5cm * 4.0cm) be dipped in the solution that cuts, take out from glove box the sealing back, at room temperature be uviol lamp (ultraviolet light dominant wavelength the is distributed in 300-360nm) irradiation 0.5 hour of 500W with power, the distance of uviol lamp and quartz container is 20cm, the final water white transparency that forms, have certain viscosity and mobile colloidal fluid, move in the glove box again.Take out barrier film with negative electrode and anodically-bonded and separate from the colloidal polymer electrolyte, be assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2, the preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 10]
By electrolyte and 10: 1 proportioning of MMA volume ratio electrolyte, MMA are mixed into homogeneous phase solution in the quartz container of cleaning, with the barrier film (5.5cm * 4.0cm) be dipped in the solution that cuts, take out from glove box the sealing back, at room temperature be uviol lamp (ultraviolet light dominant wavelength the is distributed in 300-360nm) irradiation 2.0 hours of 500W with power, the distance of uviol lamp and quartz container is 20cm, the final colloidal fluid that forms water white transparency, has certain viscosity and flowability moves in the glove box again.Take out barrier film with negative electrode and anodically-bonded and separate from the colloidal polymer electrolyte, be assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2, the preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 11]
50: 1 proportioning of weight ratio by electrolyte and MMA volume ratio 10: 1, MMA and light trigger benzophenone (BP) is mixed into homogeneous phase solution with electrolyte, MMA, BP in the quartz container of cleaning, take out from glove box the sealing back, at room temperature be uviol lamp (ultraviolet light dominant wavelength the is distributed in 300-360nm) irradiation 0.5 hour of 500W with power, the distance of uviol lamp and quartz container is 20cm, the final colloidal fluid that forms water white transparency, has certain viscosity and flowability moves in the glove box again.(5.5cm * 4.0cm) dipping took out after 5 hours in the colloidal polymer electrolyte the barrier film that cuts, with negative electrode and anodically-bonded and separate, be assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2, the preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 12]
By electrolyte and 10: 1 proportioning of MMA volume ratio electrolyte, MMA are mixed into homogeneous phase solution in the quartz container of cleaning, take out from glove box the sealing back, at room temperature be uviol lamp (ultraviolet light dominant wavelength the is distributed in 300-360nm) irradiation 2.0 hours of 500W with power, the distance of uviol lamp and quartz container is 20cm, the final colloidal fluid that forms water white transparency, has certain viscosity and flowability moves in the glove box again.(5.5cm * 4.0cm) dipping took out after 5 hours in the colloidal polymer electrolyte the barrier film that cuts, with negative electrode and anodically-bonded and separate, be assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2, the preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 13]
100: 1 proportioning of weight ratio by electrolyte and butyl methacrylate (BMA) volume ratio 10: 1, BMA and AIBN is mixed into homogeneous phase solution with electrolyte, BMA, AIBN in the glass container of cleaning.The preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 14]
100: 1 proportioning of weight ratio by electrolyte and BMA volume ratio 10: 1, BMA and AIBN is mixed into homogeneous phase solution with electrolyte, BMA, AIBN in the glass container of cleaning, 70 ℃ baking oven polymerization 12 hours is taken out and placed in sealing back from glove box, form water white transparency, have certain viscosity and mobile colloidal fluid, move in the glove box again.(5.5cm * 4.0cm) immerses in the colloidal polymer electrolyte and takes out after 5 hours, and is bonding and separate pole piece, is assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2 with the barrier film that cuts.The preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 15]
By electrolyte and 10: 1 proportioning of BMA volume ratio electrolyte, BMA are mixed into solution in the glass container of cleaning, 80 ℃ baking oven polymerization 24 hours is taken out and placed in sealing back from glove box, form water white transparency, have certain viscosity and mobile colloidal fluid, move in the glove box again.(5.5cm * 4.0cm) immerses in the colloidal polymer electrolyte and takes out after 5 hours, and is bonding and separate pole piece, is assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2 with the barrier film that cuts.The preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 16]
By electrolyte and 10: 1 proportioning of BMA volume ratio electrolyte, BMA are mixed into solution in the glass container of cleaning, with the barrier film (5.5cm * 4.0cm) be dipped in the solution that cuts, 80 ℃ baking oven polymerization 24 hours is taken out and placed in sealing back from glove box, form water white transparency, have certain viscosity and mobile colloidal fluid, move into glove box again.From the colloidal polymer electrolyte, take out barrier film with negative electrode and anodically-bonded and separate, be assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2.The preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 17]
Pressed electrolyte and BMA volume ratio 10: 1,50: 1 the proportioning of weight ratio of BMA and light trigger benzophenone (BP) is with electrolyte, BMA, BP is mixed into homogeneous phase solution in the quartz container of cleaning, (5.5cm * 4.0cm) barrier film is dipped in the solution with the barrier film that cuts, take out from glove box the sealing back, at room temperature be uviol lamp (ultraviolet light dominant wavelength the is distributed in 300-360nm) irradiation 0.5 hour of 500W with power, the distance of uviol lamp and quartz container is 20cm, the final water white transparency that forms, have certain viscosity and mobile colloidal fluid, move in the glove box again.Take out barrier film with negative electrode and anodically-bonded and separate from the colloidal polymer electrolyte, be assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2, the preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 18]
By electrolyte and 10: 1 proportioning of BMA volume ratio electrolyte, BMA are mixed into homogeneous phase solution in the quartz container of cleaning, with the barrier film (5.5cm * 4.0cm) be dipped in the solution that cuts, take out from glove box the sealing back, at room temperature be uviol lamp (ultraviolet light dominant wavelength the is distributed in 300-360nm) irradiation 2.0 hours of 500W with power, the distance of uviol lamp and quartz container is 20cm, the final colloidal fluid that forms water white transparency, has certain viscosity and flowability moves in the glove box again.Take out barrier film with negative electrode and anodically-bonded and separate from the colloidal polymer electrolyte, be assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2, the preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 19]
50: 1 proportioning of weight ratio by electrolyte and BMA volume ratio 10: 1, BMA and light trigger benzophenone (BP) is mixed into homogeneous phase solution with electrolyte, BMA, BP in the quartz container of cleaning, take out from glove box the sealing back, at room temperature be uviol lamp (ultraviolet light dominant wavelength the is distributed in 300-360nm) irradiation 0.5 hour of 500W with power, the distance of uviol lamp and quartz container is 20cm, the final colloidal fluid that forms water white transparency, has certain viscosity and flowability moves in the glove box again.(5.5cm * 4.0cm) dipping took out after 5 hours in the colloidal polymer electrolyte the barrier film that cuts, with negative electrode and anodically-bonded and separate, be assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2, the preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 20]
By electrolyte and 10: 1 proportioning of BMA volume ratio electrolyte, BMA are mixed into homogeneous phase solution in the quartz container of cleaning, take out from glove box the sealing back, at room temperature be uviol lamp (ultraviolet light dominant wavelength the is distributed in 300-360nm) irradiation 2.0 hours of 500W with power, the distance of uviol lamp and quartz container is 20cm, the final colloidal fluid that forms water white transparency, has certain viscosity and flowability moves in the glove box again.(5.5cm * 4.0cm) dipping took out after 5 hours in the colloidal polymer electrolyte the barrier film that cuts, with negative electrode and anodically-bonded and separate, be assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2, the preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 21]
The preparation condition of negative electrode, anode is with embodiment four.100: 1 proportioning of weight ratio by electrolyte and BMA volume ratio 10: 1, BMA and AIBN is mixed into homogeneous phase solution with electrolyte, BMA, AIBN in the glass container of cleaning.With the area that cuts is 22cm
2(barrier film of 5.5cm * 4.0cm) separates negative electrode and anode, be assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2, before the packaging bag sealing, mixed solution is injected packaging bag, the barrier film and the pole piece that fold are fully soaked, then with the packaging bag sealed after being vacuumized, from glove box, take out and place 70 ℃ baking oven polymerization 12 hours, make the multilayer folding Experimental cell.The test condition of battery is with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 22]
100: 1 proportioning of weight ratio by electrolyte and butyl acrylate (BA) volume ratio 10: 1, BA and AIBN is mixed into homogeneous phase solution with electrolyte, BA, AIBN in the glass container of cleaning.The preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 23]
100: 1 proportioning of weight ratio by electrolyte and BA volume ratio 10: 1, BA and AIBN is mixed into homogeneous phase solution with electrolyte, BA, AIBN in the glass container of cleaning, 70 ℃ baking oven polymerization 12 hours is taken out and placed in sealing back from glove box, form water white transparency, have certain viscosity and mobile colloidal fluid, move in the glove box again.(5.5cm * 4.0cm) immerses in the colloidal polymer electrolyte and takes out after 5 hours, and is bonding and separate pole piece, is assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2 with the barrier film that cuts.The preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 24]
By electrolyte and 10: 1 proportioning of BA volume ratio electrolyte, BA are mixed into solution in the glass container of cleaning, 80 ℃ baking oven polymerization 24 hours is taken out and placed in sealing back from glove box, form water white transparency, have certain viscosity and mobile colloidal fluid, move in the glove box again.(5.5cm * 4.0cm) immerses in the colloidal polymer electrolyte and takes out after 5 hours, and is bonding and separate pole piece, is assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2 with the barrier film that cuts.The preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 25]
By electrolyte and 10: 1 proportioning of BA volume ratio electrolyte, BA are mixed into solution in the glass container of cleaning, with the barrier film (5.5cm * 4.0cm) be dipped in the solution that cuts, 80 ℃ baking oven polymerization 24 hours is taken out and placed in sealing back from glove box, form water white transparency, have certain viscosity and mobile colloidal fluid, move into glove box again.From the colloidal polymer electrolyte, take out barrier film with negative electrode and anodically-bonded and separate, be assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2.The preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 26]
Pressed electrolyte and BA volume ratio 10: 1,50: 1 the proportioning of weight ratio of BA and light trigger benzophenone (BP) is with electrolyte, BA, BP is mixed into homogeneous phase solution in the quartz container of cleaning, (5.5cm * 4.0cm) barrier film is dipped in the solution with the barrier film that cuts, take out from glove box the sealing back, at room temperature be uviol lamp (ultraviolet light dominant wavelength the is distributed in 300-360nm) irradiation 0.5 hour of 500W with power, the distance of uviol lamp and quartz container is 20cm, the final water white transparency that forms, have certain viscosity and mobile colloidal fluid, move in the glove box again.Take out barrier film with negative electrode and anodically-bonded and separate from the colloidal polymer electrolyte, be assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2, the preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 27]
By electrolyte and 10: 1 proportioning of BA volume ratio electrolyte, BA are mixed into homogeneous phase solution in the quartz container of cleaning, with the barrier film (5.5cm * 4.0cm) be dipped in the solution that cuts, take out from glove box the sealing back, at room temperature be uviol lamp (ultraviolet light dominant wavelength the is distributed in 300-360nm) irradiation 2.0 hours of 500W with power, the distance of uviol lamp and quartz container is 20cm, the final colloidal fluid that forms water white transparency, has certain viscosity and flowability moves in the glove box again.Take out barrier film with negative electrode and anodically-bonded and separate from the colloidal polymer electrolyte, be assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2, the preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 28]
50: 1 proportioning of weight ratio by electrolyte and BA volume ratio 10: 1, BA and light trigger benzophenone (BP) is mixed into homogeneous phase solution with electrolyte, BA, BP in the quartz container of cleaning, take out from glove box the sealing back, at room temperature be uviol lamp (ultraviolet light dominant wavelength the is distributed in 300-360nm) irradiation 0.5 hour of 500W with power, the distance of uviol lamp and quartz container is 20cm, the final colloidal fluid that forms water white transparency, has certain viscosity and flowability moves in the glove box again.(5.5cm * 4.0cm) dipping took out after 5 hours in the colloidal polymer electrolyte the barrier film that cuts, with negative electrode and anodically-bonded and separate, be assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2, the preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 29]
By electrolyte and 10: 1 proportioning of BA volume ratio electrolyte, BA are mixed into homogeneous phase solution in the quartz container of cleaning, take out from glove box the sealing back, at room temperature be uviol lamp (ultraviolet light dominant wavelength the is distributed in 300-360nm) irradiation 2.0 hours of 500W with power, the distance of uviol lamp and quartz container is 20cm, the final colloidal fluid that forms water white transparency, has certain viscosity and flowability moves in the glove box again.(5.5cm * 4.0cm) dipping took out after 5 hours in the colloidal polymer electrolyte the barrier film that cuts, with negative electrode and anodically-bonded and separate, be assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2, the preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 30]
The preparation condition of negative electrode, anode is with embodiment four.100: 1 proportioning of weight ratio by electrolyte and BA volume ratio 10: 1, BA and AIBN is mixed into homogeneous phase solution with electrolyte, BA, AIBN in the glass container of cleaning.With the area that cuts is that (barrier film of 5.5cm * 4.0cm) separates negative electrode and anode to 22cm2, be assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2, before the packaging bag sealing, mixed solution is injected packaging bag, the barrier film and the pole piece that fold are fully soaked, then packaging bag is sealed, from glove box, take out and place 70 ℃ baking oven polymerization 12 hours, make the multilayer folding Experimental cell.The test condition of battery is with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 31]
100: 1 proportioning of weight ratio by electrolyte and methyl acrylate (MA) volume ratio 10: 1, MA and AIBN is mixed into homogeneous phase solution with electrolyte, MA, AIBN in the glass container of cleaning.The preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 32]
100: 1 proportioning of weight ratio by electrolyte and MA volume ratio 10: 1, MA and AIBN is mixed into homogeneous phase solution with electrolyte, MA, AIBN in the glass container of cleaning, 70 ℃ baking oven polymerization 12 hours is taken out and placed in sealing back from glove box, form water white transparency, have certain viscosity and mobile colloidal fluid, move in the glove box again.(5.5cm * 4.0cm) immerses in the colloidal polymer electrolyte and takes out after 5 hours, and is bonding and separate pole piece, is assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2 with the barrier film that cuts.The preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 33]
By electrolyte and 10: 1 proportioning of MA volume ratio electrolyte, MA are mixed into solution in the glass container of cleaning, 80 ℃ baking oven polymerization 24 hours is taken out and placed in sealing back from glove box, form water white transparency, have certain viscosity and mobile colloidal fluid, move in the glove box again.(5.5cm * 4.0cm) immerses in the colloidal polymer electrolyte and takes out after 5 hours, and is bonding and separate pole piece, is assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2 with the barrier film that cuts.The preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 34]
By electrolyte and 10: 1 proportioning of MA volume ratio electrolyte, MA are mixed into solution in the glass container of cleaning, with the barrier film (5.5cm * 4.0cm) be dipped in the solution that cuts, 80 ℃ baking oven polymerization 24 hours is taken out and placed in sealing back from glove box, form water white transparency, have certain viscosity and mobile colloidal fluid, move into glove box again.From the colloidal polymer electrolyte, take out barrier film with negative electrode and anodically-bonded and separate, be assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2.The preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 35]
Pressed electrolyte and MA volume ratio 10: 1,50: 1 the proportioning of weight ratio of MA and light trigger benzophenone (BP) is with electrolyte, MA, BP is mixed into homogeneous phase solution in the quartz container of cleaning, (5.5cm * 4.0cm) barrier film is dipped in the solution with the barrier film that cuts, take out from glove box the sealing back, at room temperature be uviol lamp (ultraviolet light dominant wavelength the is distributed in 300-360nm) irradiation 0.5 hour of 500W with power, the distance of uviol lamp and quartz container is 20cm, the final water white transparency that forms, have certain viscosity and mobile colloidal fluid, move in the glove box again.Take out barrier film with negative electrode and anodically-bonded and separate from the colloidal polymer electrolyte, be assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2, the preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 36]
By electrolyte and 10: 1 proportioning of MA volume ratio electrolyte, MA are mixed into homogeneous phase solution in the quartz container of cleaning, with the barrier film (5.5cm * 4.0cm) be dipped in the solution that cuts, take out from glove box the sealing back, at room temperature be uviol lamp (ultraviolet light dominant wavelength the is distributed in 300-360nm) irradiation 2.0 hours of 500W with power, the distance of uviol lamp and quartz container is 20cm, the final colloidal fluid that forms water white transparency, has certain viscosity and flowability moves in the glove box again.Take out barrier film with negative electrode and anodically-bonded and separate from the colloidal polymer electrolyte, be assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2, the preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 37]
50: 1 proportioning of weight ratio by electrolyte and MA volume ratio 10: 1, MA and light trigger benzophenone (Bp) is mixed into homogeneous phase solution with electrolyte, MA, BP in the quartz container of cleaning, take out from glove box the sealing back, at room temperature be uviol lamp (ultraviolet light dominant wavelength the is distributed in 300-360nm) irradiation 0.5 hour of 500W with power, the distance of uviol lamp and quartz container is 20cm, the final colloidal fluid that forms water white transparency, has certain viscosity and flowability moves in the glove box again.(5.5cm * 4.0cm) dipping took out after 5 hours in the colloidal polymer electrolyte the barrier film that cuts, with negative electrode and anodically-bonded and separate, be assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2, the preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 38]
By electrolyte and 10: 1 proportioning of MA volume ratio electrolyte, MA are mixed into homogeneous phase solution in the quartz container of cleaning, take out from glove box the sealing back, at room temperature be uviol lamp (ultraviolet light dominant wavelength the is distributed in 300-360nm) irradiation 2.0 hours of 500W with power, the distance of uviol lamp and quartz container is 20cm, the final colloidal fluid that forms water white transparency, has certain viscosity and flowability moves in the glove box again.(5.5cm * 4.0cm) dipping took out after 5 hours in the colloidal polymer electrolyte the barrier film that cuts, with negative electrode and anodically-bonded and separate, be assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2, the preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 39]
The preparation condition of negative electrode, anode is with embodiment four.100: 1 proportioning of weight ratio by electrolyte and MA volume ratio 10: 1, MA and AIBN is mixed into homogeneous phase solution with electrolyte, MA, AIBN in the glass container of cleaning.With the area that cuts is that (barrier film of 5.5cm * 4.0cm) separates negative electrode and anode to 22cm2, be assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2, before the packaging bag sealing, mixed solution is injected packaging bag, the barrier film and the pole piece that fold are fully soaked, then with the packaging bag sealed after being vacuumized, from glove box, take out and place 70 ℃ baking oven polymerization 12 hours, make the multilayer folding Experimental cell.The test condition of battery is with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 40]
100: 1 proportioning of weight ratio by electrolyte and methyl methacrylate (MMA) volume ratio 10: 1, MMA and AIBN is mixed into homogeneous phase solution with electrolyte, MMA, AIBN in the glass container of cleaning, be 22cm with the area that cuts
2(the PVDF paraphase barrier film of 5.5cm * 4.0cm) immerses solution, and 70 ℃ baking oven polymerization 12 hours is taken out and placed in the sealing back from glove box, form water white transparency, have certain viscosity and mobile colloidal fluid.The preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 41]
100: 1 proportioning of weight ratio by electrolyte and MMA volume ratio 10: 1, MMA and AIBN is mixed into homogeneous phase solution with electrolyte, MMA, AIBN in the glass container of cleaning, 70 ℃ baking oven polymerization 12 hours is taken out and placed in sealing back from glove box, form water white transparency, have certain viscosity and mobile colloidal fluid, move in the glove box again.(5.5cm * 4.0cm) immerses in the colloidal polymer electrolyte and takes out after 5 hours, and is bonding and separate pole piece, is assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2 with the PVDF paraphase barrier film that cuts.The preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 42]
By electrolyte and 10: 1 proportioning of MMA volume ratio electrolyte, MMA are mixed into solution in the glass container of cleaning, 80 ℃ baking oven polymerization 24 hours is taken out and placed in sealing back from glove box, form water white transparency, have certain viscosity and mobile colloidal fluid, move in the glove box again.(5.5cm * 4.0cm) immerses in the colloidal polymer electrolyte and takes out after 5 hours, and is bonding and separate pole piece, is assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2 with the PVDF paraphase barrier film that cuts.The preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 43]
By electrolyte and 10: 1 proportioning of MMA volume ratio electrolyte, MMA are mixed into solution in the glass container of cleaning, with the PVDF paraphase barrier film (5.5cm * 4.0cm) be dipped in the solution that cuts, 80 ℃ baking oven polymerization 24 hours is taken out and placed in sealing back from glove box, form water white transparency, have certain viscosity and mobile colloidal fluid, move into glove box again.From the colloidal polymer electrolyte, take out barrier film with negative electrode and anodically-bonded and separate, be assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2.The preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 44]
Pressed electrolyte and MMA volume ratio 10: 1,50: 1 the proportioning of weight ratio of MMA and light trigger benzophenone (BP) is with electrolyte, MMA, BP is mixed into homogeneous phase solution in the quartz container of cleaning, with the PVDF paraphase barrier film (5.5cm * 4.0cm) be dipped in the solution that cuts, take out from glove box the sealing back, at room temperature be uviol lamp (ultraviolet light dominant wavelength the is distributed in 300-360nm) irradiation 0.5 hour of 500W with power, the distance of uviol lamp and quartz container is 20cm, the final water white transparency that forms, have certain viscosity and mobile colloidal fluid, move in the glove box again.Take out barrier film with negative electrode and anodically-bonded and separate from the colloidal polymer electrolyte, be assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2, the preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 45]
By electrolyte and 10: 1 proportioning of MMA volume ratio electrolyte, MMA are mixed into homogeneous phase solution in the quartz container of cleaning, with the PVDF paraphase barrier film (5.5cm * 4.0cm) be dipped in the solution that cuts, take out from glove box the sealing back, at room temperature be uviol lamp (ultraviolet light dominant wavelength the is distributed in 300-360nm) irradiation 2.0 hours of 500W with power, the distance of uviol lamp and quartz container is 20cm, the final colloidal fluid that forms water white transparency, has certain viscosity and flowability moves in the glove box again.Take out barrier film with negative electrode and anodically-bonded and separate from the colloidal polymer electrolyte, be assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2, the preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 46]
50: 1 proportioning of weight ratio by electrolyte and MMA volume ratio 10: 1, MMA and light trigger benzophenone (BP) is mixed into homogeneous phase solution with electrolyte, MA, BP in the quartz container of cleaning, take out from glove box the sealing back, at room temperature be uviol lamp (ultraviolet light dominant wavelength the is distributed in 300-360nm) irradiation 0.5 hour of 500W with power, the distance of uviol lamp and quartz container is 20cm, the final colloidal fluid that forms water white transparency, has certain viscosity and flowability moves in the glove box again.(5.5cm * 4.0cm) dipping took out after 5 hours in the colloidal polymer electrolyte the PVDF paraphase barrier film that cuts, with negative electrode and anodically-bonded and separate, be assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2, the preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 47]
By electrolyte and 10: 1 proportioning of MMA volume ratio electrolyte, MMA are mixed into homogeneous phase solution in the quartz container of cleaning, take out from glove box the sealing back, at room temperature be uviol lamp (ultraviolet light dominant wavelength the is distributed in 300-360nm) irradiation 2.0 hours of 500W with power, the distance of uviol lamp and quartz container is 20cm, the final colloidal fluid that forms water white transparency, has certain viscosity and flowability moves in the glove box again.The PVDF paraphase that cuts every (dipping in the colloidal polymer electrolyte of 5.5cm * 4.0cm) took out after 5 hours, with negative electrode and anodically-bonded and separate, be assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2, the preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 48]
The preparation condition of negative electrode, anode is with embodiment four.100: 1 proportioning of weight ratio by electrolyte and MMA volume ratio 10: 1, MMA and AIBN is mixed into homogeneous phase solution with electrolyte, MMA, AIBN in the glass container of cleaning.With the area that cuts is 22cm
2(the PVDF paraphase barrier film of 5.5cm * 4.0cm) separates negative electrode and anode, be assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2, before the packaging bag sealing, mixed solution is injected packaging bag, the barrier film and the pole piece that fold are fully soaked, then packaging bag is sealed, from glove box, take out and place 70 ℃ baking oven polymerization 12 hours, make the multilayer folding Experimental cell.The test condition of battery is with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 49] are mixed into solution with electrolyte, MMA by electrolyte and 10: 1 proportioning of MMA volume ratio in the glass container of cleaning, with the PVDF paraphase barrier film (5.5cm * 4.0cm) be dipped in the solution that cuts, sealing back is taken out from glove box and placed irradiation intensity is irradiation 0.1 hour under the gamma-rays of 60Gy, form water white transparency, have certain viscosity and mobile colloidal fluid, move into glove box again.From the colloidal polymer electrolyte, take out barrier film with negative electrode and anodically-bonded and separate, be assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2.The preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.Discharging and recharging data lists in the subordinate list 1.[embodiment 50] are mixed into solution with electrolyte, MA by electrolyte and 10: 1 proportioning of MA volume ratio in the glass container of cleaning, with the PVDF paraphase barrier film (5.5cm * 4.0cm) be dipped in the solution that cuts, sealing back is taken out from glove box and placed irradiation intensity is irradiation 0.1 hour under the gamma-rays of 60Gy, form water white transparency, have certain viscosity and mobile colloidal fluid, move into glove box again.From the colloidal polymer electrolyte, take out barrier film with negative electrode and anodically-bonded and separate, be assembled into the multilayer folding Experimental cell by shown in the accompanying drawing 2.The preparation of all the other negative electrodes, anode and the assembling of Experimental cell and test condition are with embodiment four.Discharging and recharging data lists in the subordinate list 1.
Table .1 embodiment numbers reversible capacity cyclicity parameter first all efficient second all efficient
(mAh/g) (％) (％)
1 92 -0.32 74 91
2 97 -0.35 70 91
3 124 -0.11 88 99
4 125 -0.03 88 99
5 122 -0.15 88 92
6 87 -0.05 60 90
7 102 -0.07 81 98
8 67 -0.33 77 98
9 89 -0.19 70 94
10 85 -0.10 75 95
11 92 -0.12 77 93
12 76 -0.21 81 91
13 112 -0.15 82 93
14 106 -0.13 79 96
15 120 -0.08 85 96
16 98 -0.20 72 92
17 85 -0.25 71 90
18 90 -0.18 76 95
19 106 -0.07 82 94
20 100 -0.12 86 93
21 70 -0.41 70 90
22 111 -0.16 75 92
23 102 -0.23 81 89
24 109 -0.19 82 93
25 98 -0.30 77 90
26 88 -0.42 75 88
27 93 -0.37 72 91
28 102 -0.10 80 89
29 87 -0.35 70 85
30 121 -0.12 80 91
31 116 -0.15 81 93
32 108 -0.09 79 94
33 114 -0.06 82 96
34 102 -0.12 77 89
35 98 -0.45 75 86
36 89 -0.39 71 82
37 87 -0.28 73 84
38 93 -0.47 70 81
39 78 -0.53 69 86
40 126 -0.02 87 98
41 123 -0.02 85 99
42 118 -0.03 84 97
43 120 -0.11 86 96
44 113 -0.09 82 97
45 119 -0.07 80 93
46 109 -0.06 79 92
47 123 -0.19 83 94
48 102 -0.23 78 90
49 98 -0.35 77 90
50 106 -0.27 80 93
Claims (14)
1. one kind is electrolytical secondary lithium battery with colloidal polymer, it is characterized in that: by being the anode of active material with the material with carbon element, with the transition metal oxide that contains lithium is the negative electrode of active material, with the colloidal polymer is electrolyte, membrane for polymer, composite film packaging bag, lead-in wire, fluid sealant is formed secondary lithium battery
Wherein being used to prepare electrolytical each component material of colloidal polymer comprises: (1) polymerization single polymerization monomer: for carrying out the acrylic ester monomer of radical polymerization or ionic polymerization, (2) electrolyte: the mixed solvent of being made up of a kind of solvent or several organic solvent adds one or more solubility lithium salts and forms
(3) initator: adopt one or more thermal initiators or light trigger or do not use initator, (4) membrane for polymer;
The weight ratio 50 of described electrolyte and polymerization single polymerization monomer volume ratio 10: 1, polymerization single polymerization monomer and initator: 1-100: 1.
2. described by claim 1 is electrolytical secondary lithium battery with colloidal polymer, and it is characterized in that: described active material of cathode is selected from LiCoO
2, LiNiO
2Or LiMn
2O
4
3. described by claim 1 is electrolytical secondary lithium battery with colloidal polymer, and it is characterized in that: active material of positive electrode is selected from soft carbon or hard carbon.
4. described by claim 1 is electrolytical secondary lithium battery with colloidal polymer, and it is characterized in that: used polymerization single polymerization monomer is selected from methyl methacrylate, EMA, propyl methacrylate, isobutyl methacrylate, butyl methacrylate, EHMA, allyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, alkoxyl (contracting) diethylene glycol monoacrylate, (contracting) glycol diacrylate, alkoxyl (contracting) ethylene glycol methacrylate or (contracting) ethylene glycol dimethacrylate.
5. described by claim 1 is electrolytical secondary lithium battery with colloidal polymer, and it is characterized in that: the organic solvent of used electrolyte is selected from vinyl carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl-methyl carbonic ester or dimethoxy-ethane; The solubility lithium salts is selected from LiN (CF
3SO
2)
3, LiClO
4, LiBF
4, LiPF
6, LiCF
3SO
3, LiN (CF
3SO
2)
2Or LiAsF
6
6. described by claim 1 is electrolytical secondary lithium battery with colloidal polymer, and it is characterized in that: used thermal initiator has (1) azo-initiator: be selected from azobisisobutyronitrile or azo two eyeball in different heptan; (2) peroxide initator: dialkyl peroxide is selected from di-tert-butyl peroxide or cumyl peroxide, peroxidating two acyls are selected from dibenzoyl peroxide or dilauroyl peroxide, organic hydroperoxide is selected from isopropyl benzene hydroperoxide, and peroxy dicarbonate is selected from di-isopropyl peroxydicarbonate or di-cyclohexylperoxy di-carbonate; (3) redox initiation system: as the tertiary amine that comprises of reducing agent, naphthenate, organo-metallic compound, boron triethyl, redox initiation system are selected from dibenzoyl peroxide and N, the initiator system that accelerine is formed.
7. described by claim 1 is electrolytical secondary lithium battery with colloidal polymer, it is characterized in that: used light trigger has (1) styrax ethers initator: be selected from benzoin isobutyl butyl ether, benzoin isobutyl propyl group ether, benzoin methyl ether or benzoin ethyl ether; (2) ketone and derivative thereof or ketone-amine system initator: be selected from benzophenone, 4,4 '-(N, TMSDMA N dimethylamine base) benzophenone, acetophenone, diethoxy acetophenone, isopropyl thioxanthone, 2-methyl thioxanthone or xanthone; (3) benzil and acetals initator; (4) fused ring compound derivatives class initator extremely: be selected from naphthalene and acetonaphthone, quinones, anthracene class or pyrene; (5) the monoxime ester class initator of alkyl-phenyl ketone: be selected from diacetyl monoxime ester or benzil monoxime ester; (6) azo-initiator.
8. described by claim 1 is electrolytical secondary lithium battery with colloidal polymer, and it is characterized in that: used membrane for polymer is selected from (1) general porous polypropylene film, porous polyethylene membrane and composite membrane thereof; (2) porous Kynoar paraphase film or noninvert film; (3) the porous polyoxyethylene film of porous polypropylene eyeball film or (4) fiber or powder enhancing.
9. one kind is the preparation method of electrolytical secondary lithium battery with colloidal polymer, it is characterized in that:
The electrolyte of preparation colloidal polymer may further comprise the steps:
(1) with the polymerization single polymerization monomer rectification and purification, divide anhydrate branch and other impurity,
(2) be that moisture was removed in oven dry in 12-24 hour in the vacuum drying oven of 0.1Mpa with initator and membrane for polymer at 5-30 ℃, vacuum degree,
(3) mentioned component is moved into together water content and is lower than in the inert atmosphere glove box of 1.0ppm,
(4) by electrolyte and polymerization single polymerization monomer with volume ratio 10: 1, polymerization single polymerization monomer and initator with weight ratio 50: 1-100: 1 proportioning is mixed into homogeneous phase solution with electrolyte, polymerization single polymerization monomer, initator in the glass container of cleaning,
(5) membrane for polymer is immersed above-mentioned mixed solution,
(6) above-mentioned system sealing back is taken out from glove box, and place 0 ℃-100 ℃ baking oven polymerase 10 .1 hour-15 hours, forms colloidal fluid water white, that have certain viscosity and flowability;
The preparation method of negative electrode pole piece is as follows: with active material of cathode, the conductive additive powder, its granularity 1-1000nm, comprise acetylene black, carbon black, graphite powder, various oxides, sulfide or halide powder, bonding agent, it comprises the dimethyl formamide solution of certain density vinylidene fluoride-hexafluoropropylene copolymer, mix, make the composite mortar of homogeneous at normal temperatures and pressures, slurry evenly is coated in aluminium foil as collector, on its thickness 15-20um, then 100-160 ℃ of oven dry down, the gained film thickness is at 50-100um, through densification, continue to dry by the fire 12 hours down, in the pole piece after the oven dry then at 100-160 ℃, cathode active material accounts for the 85wt% that always is coated with application, copolymer comprised 5wt%, dispersant accounts for 10wt%, both cathode material can be coated in the single face of aluminium foil, also can be coated in the two-sided of aluminium foil, then the gained pole piece is cut into required form by the battery specification for preparing and be negative electrode;
The preparation method of anode is as follows: with material with carbon element and bonding agent, it comprises the dimethyl formamide solution of certain density Kynoar, be mixed and made into the compound slurry of homogeneous, evenly be coated on the collector then, collector can be the paper tinsel of various conductions, the net porous body, foams or corpus fibrosum carrier, gained film thickness 40-90um, 100-160 ℃ of oven dry down, then through densification, continuation was dried by the fire 12 hours down at 100-160 ℃, in the pole piece after the oven dry, anode active material accounts for the 94wt% that always is coated with application, and bonding agent accounts for 6wt%, both anode material can be coated in the single face of Copper Foil, also can be coated in the two-sided of Copper Foil, then the gained pole piece is cut into required form by the battery specification for preparing and be anode;
Anode and negative electrode both can be in advance can not flood with the electrolyte dipping yet, and be bonding and separate with the abundant electrolytical barrier film of colloidal polymer that floods anode and negative electrode in glove box, draws two lead-in wires respectively from the same end of negative electrode and anode.It is bonding that negative electrode and anode both can individual layers, bonding after also can multilayer folding, in the packaging bag that the aluminium/polyethylene composite film of packing into is then made, draws two lead-in wires from openend, vacuumizes the back hot sealing.
10. one kind is the preparation method of electrolytical secondary lithium battery with colloidal polymer, it is characterized in that:
The electrolyte of preparation colloidal polymer may further comprise the steps:
(1) polymerization single polymerization monomer rectification and purification is divided anhydrate branch and other impurity,
(2) be that moisture was removed in oven dry in 12-24 hour in the vacuum drying oven of 0.1Mpa with membrane for polymer at 5-30 ℃, vacuum degree,
(3) mentioned component is moved into together water content and is lower than in the inert atmosphere glove box of 1.0ppm,
(4) with 10: 1 proportioning of volume ratio electrolyte, polymerization single polymerization monomer are mixed into homogeneous phase solution by electrolyte and polymerization single polymerization monomer in the glass container of cleaning,
(5) membrane for polymer is immersed above-mentioned mixed solution,
(6) above-mentioned system sealing back is taken out from glove box, and place 80 ℃ baking oven polymerization 24 hours, forms colloidal fluid water white, that have certain viscosity and flowability;
The preparation method of negative electrode pole piece is as follows: with active material of cathode, the conductive additive powder, bonding agent mixes, make the composite mortar of homogeneous at normal temperatures and pressures, evenly be coated in slurry as collector, on the thick aluminium foil of 15-20um, then 100-160 ℃ of oven dry down, the gained film thickness is at 50-100um, then through densification, continuation was dried by the fire 12 hours down at 100-160 ℃, in the pole piece after the oven dry, cathode active material accounts for the 85wt% that always is coated with application, copolymer comprised 5wt%, dispersant accounts for 10wt%, both cathode material can be coated in the single face of aluminium foil, also can be coated in the two-sided of aluminium foil, and then the gained pole piece had been cut into required form by the battery specification for preparing and be negative electrode; The granularity of described conductive additive powder is 1-1000nm, comprises acetylene black, carbon black, graphite powder, various oxide, sulfide or halide powder; Described bonding agent comprises the dimethyl formamide solution of vinylidene fluoride-hexafluoropropylene copolymer;
The preparation method of anode is as follows: the compound slurry that material with carbon element and bonding agent is mixed and made into homogeneous, evenly be coated on the collector then, make the 40-90um thick film, under 100-160 ℃, dry by the fire in, then through densification, continuation was dried by the fire 12 hours down at 100-160 ℃, in the pole piece after the oven dry, anode active material accounts for the 94wt% that always is coated with application, bonding agent accounts for 6wt%, both anode material can be coated in the single face of Copper Foil, also can be coated in the two-sided of Copper Foil, and then the gained pole piece had been cut into required form by the battery specification for preparing and be anode; Described bonding agent comprises the dimethyl formamide solution of Kynoar; Described collector comprises paper tinsel, net porous body, foams or the corpus fibrosum carrier of conduction;
Anode and negative electrode both can be in advance can not flood with the electrolyte dipping yet, and be bonding and separate with the abundant electrolytical barrier film of colloidal polymer that floods anode and negative electrode in glove box, draws two lead-in wires respectively from the same end of negative electrode and anode.It is bonding that negative electrode and anode both can individual layers, bonding after also can multilayer folding, in the packaging bag that the aluminium/polyethylene composite film of packing into is then made, draws two lead-in wires from openend, vacuumizes the back hot sealing.
11. one kind is the preparation method of electrolytical secondary lithium battery with colloidal polymer, it is characterized in that:
The electrolyte of preparation colloidal polymer may further comprise the steps:
(1) with the polymerization single polymerization monomer rectification and purification, divide anhydrate branch and other impurity,
(2) be that moisture was removed in oven dry in 12-24 hour in the vacuum drying oven of 0.1Mpa with membrane for polymer at 5-30 ℃, vacuum degree,
(3) mentioned component is moved into together water content and is lower than in the inert atmosphere glove box of 1.0ppm,
(4) by electrolyte and the polymerization single polymerization monomer weight ratio 50 with volume ratio 10: 1, polymerization single polymerization monomer and initator: 1-100: 1 proportioning is mixed into homogeneous phase solution with electrolyte, polymerization single polymerization monomer, initator in the glass container of cleaning,
(5) membrane for polymer is immersed above-mentioned mixed solution,
(6) above-mentioned system sealing back being taken out from glove box, is irradiation 0.5 hour under the uviol lamp of 500W at power, and ultraviolet light dominant wavelength is distributed in 300-360nm, forms water white transparency, has certain viscosity and mobile colloidal fluid;
The preparation method of negative electrode pole piece is as follows: with active material of cathode, the conductive additive powder, bonding agent mixes, make the composite mortar of homogeneous at normal temperatures and pressures, evenly be coated in slurry as collector, on the thick aluminium foil of 15-20um, then 100-160 ℃ of oven dry down, the gained film thickness is at 50-100um, then through densification, continuation was dried by the fire 12 hours down at 100-160 ℃, in the pole piece after the oven dry, cathode active material accounts for the 85wt% that always is coated with application, copolymer comprised 5wt%, dispersant accounts for 10wt%, both cathode material can be coated in the single face of aluminium foil, also can be coated in the two-sided of aluminium foil, and then the gained pole piece had been cut into required form by the battery specification for preparing and be negative electrode; The granularity of described conductive additive powder is 1-1000nm, comprises acetylene black, carbon black, graphite powder, various oxide, sulfide or halide powder; Described bonding agent comprises the dimethyl formamide solution of vinylidene fluoride-hexafluoropropylene copolymer;
The preparation method of anode is as follows: the compound slurry that material with carbon element and bonding agent is mixed and made into homogeneous, evenly be coated on the collector then, make the 40-90um thick film, 100-160 ℃ of oven dry down, then through densification, continuation was dried by the fire 12 hours down at 100-160 ℃, in the pole piece after the oven dry, anode active material accounts for the 94wt% that always is coated with application, bonding agent accounts for 6wt%, both anode material can be coated in the single face of Copper Foil, also can be coated in the two-sided of Copper Foil, and then the gained pole piece had been cut into required form by the battery specification for preparing and be anode; Described bonding agent comprises the dimethyl formamide solution of Kynoar; Described collector comprises paper tinsel, net porous body, foams or the corpus fibrosum carrier of conduction;
Anode and negative electrode both can be in advance can not flood with the electrolyte dipping yet, and be bonding and separate with the abundant electrolytical barrier film of colloidal polymer that floods anode and negative electrode in glove box, draws two lead-in wires respectively from the same end of negative electrode and anode.It is bonding that negative electrode and anode both can individual layers, bonding after also can multilayer folding, in the packaging bag that the aluminium/polyethylene composite film of packing into is then made, draws two lead-in wires from openend, vacuumizes the back hot sealing.
12. one kind is the preparation method of electrolytical secondary lithium battery with colloidal polymer, it is characterized in that:
The electrolyte of preparation colloidal polymer may further comprise the steps:
(1) with the polymerization single polymerization monomer rectification and purification, divide anhydrate branch and other impurity,
(2) be that moisture was removed in oven dry in 12-24 hour in the vacuum drying oven of 0.1Mpa with membrane for polymer at 5-30 ℃, vacuum degree,
(3) mentioned component is moved into together water content and is lower than in the inert atmosphere glove box of 1.0ppm,
(4) with 10: 1 proportioning of volume ratio electrolyte, polymerization single polymerization monomer are mixed into homogeneous phase solution by electrolyte and polymerization single polymerization monomer in the glass container of cleaning,
(5) membrane for polymer is immersed above-mentioned mixed solution,
(6) above-mentioned system sealing back being taken out from glove box, is irradiation 2 hours under the uviol lamp of 500W at power, and ultraviolet light dominant wavelength is distributed in 300-360nm, forms water white transparency, has certain viscosity and mobile colloidal fluid;
The preparation method of negative electrode pole piece is as follows: with active material of cathode, the conductive additive powder, bonding agent mixes, make the composite mortar of homogeneous at normal temperatures and pressures, evenly be coated in slurry as collector, on the thick aluminium foil of 15-20um, then 100-160 ℃ of oven dry down, the gained film thickness is at 50-100um, then through densification, continuation was dried by the fire 12 hours down at 100-160 ℃, in the pole piece after the oven dry, cathode active material accounts for the 85wt% that always is coated with application, copolymer comprised 5wt%, dispersant accounts for 10wt%, both cathode material can be coated in the single face of aluminium foil, also can be coated in the two-sided of aluminium foil, and then the gained pole piece had been cut into required form by the battery specification for preparing and be negative electrode; The granularity of described conductive additive powder is 1-1000nm, comprises acetylene black, carbon black, graphite powder, various oxide, sulfide or halide powder; Described bonding agent comprises the dimethyl formamide solution of vinylidene fluoride-hexafluoropropylene copolymer;
The preparation method of anode is as follows: the compound slurry that material with carbon element and bonding agent is mixed and made into homogeneous, evenly be coated on the collector then, make the 40-90um thick film, 100-160 ℃ of oven dry down, then through densification, continuation was dried by the fire 12 hours down at 100-160 ℃, in the pole piece after the oven dry, anode active material accounts for the 94wt% that always is coated with application, bonding agent accounts for 6wt%, both anode material can be coated in the single face of Copper Foil, also can be coated in the two-sided of Copper Foil, and then the gained pole piece had been cut into required form by the battery specification for preparing and be anode; Described bonding agent comprises the dimethyl formamide solution of Kynoar; Described collector comprises paper tinsel, net porous body, foams or the corpus fibrosum carrier of conduction;
Anode and negative electrode both can be in advance can not flood with the electrolyte dipping yet, and be bonding and separate with the abundant electrolytical barrier film of colloidal polymer that floods anode and negative electrode in glove box, draws two lead-in wires respectively from the same end of negative electrode and anode.It is bonding that negative electrode and anode both can individual layers, bonding after also can multilayer folding, in the packaging bag that the aluminium/polyethylene composite film of packing into is then made, draws two lead-in wires from openend, vacuumizes the back hot sealing.
13. one kind is the preparation method of electrolytical secondary lithium battery with colloidal polymer, it is characterized in that:
The electrolyte of preparation colloidal polymer may further comprise the steps:
(1) with the polymerization single polymerization monomer rectification and purification, divide anhydrate branch and other impurity,
(2) be that moisture was removed in oven dry in 12-24 hour in the vacuum drying oven of 0.1Mpa with membrane for polymer at 5-30 ℃, vacuum degree,
(3) mentioned component is moved into together water content and is lower than in the inert atmosphere glove box of 1.0ppm,
(4) with 10: 1 proportioning of volume ratio electrolyte, polymerization single polymerization monomer are mixed into homogeneous phase solution by electrolyte and polymerization single polymerization monomer in the glass container of cleaning,
(5) membrane for polymer is immersed above-mentioned mixed solution,
(6) above-mentioned system sealing back is taken out from glove box, adopt the initiation mode initiated polymerization of gamma-ray irradiation or electron beam irradiation to prepare the colloidal polymer electrolyte, exposure time 0.1 hour, irradiation intensity 60Gy forms water white transparency, has certain viscosity and mobile colloidal fluid;
The preparation method of negative electrode pole piece is as follows: with active material of cathode, the conductive additive powder, bonding agent mixes, make the composite mortar of homogeneous at normal temperatures and pressures, evenly be coated in slurry as collector, on the thick aluminium foil of 15-20um, then 100-160 ℃ of oven dry down, the gained film thickness is at 50-100um, then through densification, continuation was dried by the fire 12 hours down at 100-160 ℃, in the pole piece after the oven dry, cathode active material accounts for the 85wt% that always is coated with application, copolymer comprised 5wt%, dispersant accounts for 10wt%, both cathode material can be coated in the single face of aluminium foil, also can be coated in the two-sided of aluminium foil, and then the gained pole piece had been cut into required form by the battery specification for preparing and be negative electrode; The granularity of described conductive additive powder is 1-1000nm, comprises acetylene black, carbon black, graphite powder, various oxide, sulfide or halide powder; Described bonding agent comprises the dimethyl formamide solution of vinylidene fluoride-hexafluoropropylene copolymer;
The preparation method of anode is as follows: the compound slurry that material with carbon element and bonding agent is mixed and made into homogeneous, evenly be coated on the collector then, make the 40-90um thick film, 100-160 ℃ of oven dry down, then through densification, continuation was dried by the fire 12 hours down at 100-160 ℃, in the pole piece after the oven dry, anode active material accounts for the 94wt% that always is coated with application, bonding agent accounts for 6wt%, both anode material can be coated in the single face of Copper Foil, also can be coated in the two-sided of Copper Foil, and then the gained pole piece had been cut into required form by the battery specification for preparing and be anode; Described bonding agent comprises the dimethyl formamide solution of Kynoar; Described collector comprises paper tinsel, net porous body, foams or the corpus fibrosum carrier of conduction;
Anode and negative electrode both can be in advance can not flood with the electrolyte dipping yet, and be bonding and separate with the abundant electrolytical barrier film of colloidal polymer that floods anode and negative electrode in glove box, draws two lead-in wires respectively from the same end of negative electrode and anode.It is bonding that negative electrode and anode both can individual layers, bonding after also can multilayer folding, in the packaging bag that the aluminium/polyethylene composite film of packing into is then made, draws two lead-in wires from openend, vacuumizes the back hot sealing.
14. one kind is the preparation method of electrolytical secondary lithium battery with colloidal polymer, it is characterized in that:
The electrolyte of preparation colloidal polymer may further comprise the steps:
(1) by electrolyte and 10: 1 proportioning of polymerization single polymerization monomer volume ratio electrolyte, polymerization single polymerization monomer are mixed into homogeneous phase solution in the glass container of cleaning, aggregate into colloidal electrolyte in a usual manner;
(2) membrane for polymer was immersed above-mentioned mixed solution 5 hours, form colloidal fluid water white, that have certain viscosity and flowability;
The preparation method of negative electrode pole piece is as follows: with active material of cathode, the conductive additive powder, bonding agent mixes, make the composite mortar of homogeneous at normal temperatures and pressures, evenly be coated in slurry as collector, on the thick aluminium foil of 15-20um, then 100-160 ℃ of oven dry down, the gained film thickness is at 50-100um, then through densification, continuation was dried by the fire 12 hours down at 100-160 ℃, in the pole piece after the oven dry, cathode active material accounts for the 85wt% that always is coated with application, copolymer comprised 5wt%, dispersant accounts for 10wt%, both cathode material can be coated in the single face of aluminium foil, also can be coated in the two-sided of aluminium foil, and then the gained pole piece had been cut into required form by the battery specification for preparing and be negative electrode; The granularity of described conductive additive powder is 1-1000nm, comprises acetylene black, carbon black, graphite powder, various oxide, sulfide or halide powder; Described bonding agent comprises the dimethyl formamide solution of vinylidene fluoride-hexafluoropropylene copolymer;
The preparation method of anode is as follows: the compound slurry that material with carbon element and bonding agent is mixed and made into homogeneous, evenly be coated on the collector then, make the 40-90um thick film, 100-160 ℃ of oven dry down, then through densification, continuation was dried by the fire 12 hours down at 100-160 ℃, in the pole piece after the oven dry, anode active material accounts for the 94wt% that always is coated with application, bonding agent accounts for 6wt%, both anode material can be coated in the single face of Copper Foil, also can be coated in the two-sided of Copper Foil, and then the gained pole piece had been cut into required form by the battery specification for preparing and be anode; Described bonding agent comprises the dimethyl formamide solution of Kynoar; Described collector comprises paper tinsel, net porous body, foams or the corpus fibrosum carrier of conduction;
Anode and negative electrode both can be in advance can not flood with the electrolyte dipping yet, and be bonding and separate with the abundant electrolytical barrier film of colloidal polymer that floods anode and negative electrode in glove box, draws two lead-in wires respectively from the same end of negative electrode and anode.It is bonding that negative electrode and anode both can individual layers, bonding after also can multilayer folding, in the packaging bag that the aluminium/polyethylene composite film of packing into is then made, draws two lead-in wires from openend, vacuumizes the back hot sealing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001055410A CN1142613C (en) | 2000-03-30 | 2000-03-30 | Secondary Li ion battery using colloidal polymer as electrolyte and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001055410A CN1142613C (en) | 2000-03-30 | 2000-03-30 | Secondary Li ion battery using colloidal polymer as electrolyte and its preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1315752A CN1315752A (en) | 2001-10-03 |
| CN1142613C true CN1142613C (en) | 2004-03-17 |
Family
ID=4577758
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001055410A Expired - Fee Related CN1142613C (en) | 2000-03-30 | 2000-03-30 | Secondary Li ion battery using colloidal polymer as electrolyte and its preparing process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1142613C (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100497251B1 (en) * | 2003-08-20 | 2005-06-23 | 삼성에스디아이 주식회사 | Protective composition for negative electrode of lithium sulfur battery and lithium sulfur battery fabricated by using same |
| CN1296284C (en) * | 2004-08-09 | 2007-01-24 | 武汉大学 | Process for preparing nano metal oxide material |
| CN1303719C (en) * | 2004-12-22 | 2007-03-07 | 华南理工大学 | Production for gel polymer electrolyte |
| CN101685876B (en) * | 2008-09-27 | 2013-06-26 | 深圳市比克电池有限公司 | Preparation method of polymer battery |
| CN102064342B (en) * | 2010-12-21 | 2013-03-13 | 东莞市杉杉电池材料有限公司 | Novel lithium ion battery gel electrolyte |
| CN102354619B (en) * | 2011-09-14 | 2016-08-17 | 中国第一汽车股份有限公司 | A kind of flexible solid-state supercapacitor |
| CN102360950B (en) * | 2011-09-14 | 2017-03-15 | 中国第一汽车股份有限公司 | A kind of barrier film for flexible solid-state supercapacitor and preparation method thereof |
| CN102412378A (en) * | 2011-09-28 | 2012-04-11 | 哈尔滨工业大学 | Polymer electrolyte isolating membrane, preparation method and use thereof |
| WO2013084116A1 (en) * | 2011-12-07 | 2013-06-13 | Basf Se | Electrochemical cells comprising nitrogen-containing polymers |
| CN103413974B (en) * | 2013-07-24 | 2015-07-08 | 广东精进能源有限公司 | Preparation method of lithium ion battery gel polymer electrolyte |
| CN103700886B (en) * | 2013-12-24 | 2016-05-04 | 江苏华东锂电技术研究院有限公司 | The preparation method of polymer Li-ion battery |
| CN105578811B (en) | 2014-10-17 | 2018-09-04 | 小米科技有限责任公司 | Electronic equipment and electronic equipment application method |
| CN105590759B (en) * | 2014-10-23 | 2018-06-26 | 同济大学 | A kind of method that semiconductor self-initiating polymerization prepares ionic liquid gel electrolyte |
| CN107086123A (en) * | 2017-04-01 | 2017-08-22 | 中南大学 | Doping gel capacitor electrolyte based on photocuring and preparation method thereof |
| CN108976367B (en) * | 2018-06-07 | 2020-07-03 | 复旦大学 | Method for realizing 'active'/controllable free radical polymerization under air condition |
| CN109768280A (en) * | 2018-12-20 | 2019-05-17 | 中国科学院青岛生物能源与过程研究所 | A kind of lithium battery anode with free radical capture function |
-
2000
- 2000-03-30 CN CNB001055410A patent/CN1142613C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1315752A (en) | 2001-10-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1142613C (en) | Secondary Li ion battery using colloidal polymer as electrolyte and its preparing process | |
| CN1226802C (en) | Lithium polymer secondary cell | |
| CN1320685C (en) | Organic electrolyte and lithium secondary cell using same | |
| CN1255895C (en) | Composition for electrolyte, electrolyte and process for producing same, and cell contg. same | |
| CN1577944A (en) | Electrolyte for lithium secondary battery and lithium secondary battery comprising same | |
| CN1393954A (en) | Lithium polymer cell | |
| EP3678229A1 (en) | Anode active material and anode using same, electrochemical device and electronic device | |
| CN1841816A (en) | Negative electrode for non-aqueous secondary battery | |
| CN1325147A (en) | Solid or gel electrolyte and cells using same | |
| CN1320682C (en) | Repeatedly chargeable-dischargeable lithium ion power cell and its production method | |
| CN1428012A (en) | Nonaqueous electrolyte lithium secondary cell | |
| CN1870326A (en) | Non-aqueous solution electrochemical device polar plate and its manufacturing method | |
| CN1681145A (en) | Negative electrode active material and use of secondary lithium battery | |
| CN1302069C (en) | Polymer electrolyte, its prodcing process and lithim bottery using the same electrolyte | |
| CN1822425A (en) | Organic electrolytic solution and lithium battery employing the same | |
| JP2008066301A (en) | Organic electrolyte solution containing silane compound and lithium battery | |
| KR101511412B1 (en) | Electrode for lithium secondary battery, lithium secondary battery using the same and fabrication method thereof | |
| CN101030659A (en) | Battery | |
| CN1674348A (en) | Organic electrolytic solution and lithium battery using the same | |
| CN1795579A (en) | Nonaqueous electrolyte solution and lithium ion secondary battery | |
| CN1233058C (en) | Great-capacity polymer-lithium ion cell and its manufacture | |
| CN1442926A (en) | Non equeous electrolyte battery | |
| CN1213501C (en) | Polymer cell | |
| CN1828982A (en) | Non-aqueous electrolyte secondary battery | |
| CN1238925C (en) | Battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |