CN105576287B - Solid electrolyte lithium ion battery and preparation method thereof of the integration without interface - Google Patents

Solid electrolyte lithium ion battery and preparation method thereof of the integration without interface Download PDF

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CN105576287B
CN105576287B CN201410528674.9A CN201410528674A CN105576287B CN 105576287 B CN105576287 B CN 105576287B CN 201410528674 A CN201410528674 A CN 201410528674A CN 105576287 B CN105576287 B CN 105576287B
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solid electrolyte
lithium ion
ion battery
binder
electrode active
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CN105576287A (en
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薛立新
杜冰
聂锋
秦德君
温乐乐
王健
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Zhejiang Industrial Research Institute Development Co ltd
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Ningbo Institute of Material Technology and Engineering of CAS
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    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02E60/10Energy storage using batteries
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract

The present invention provides a kind of integrated solid electrolyte lithium ion batteries without interface, binders for electrodes in its solid electrolyte lithium ion battery contains same material component with solid electrolyte material, particularly preferably contains fluorine-containing sulfimide moiety polymeric material components of the same race.There is good compatibility between electrolyte and electrode material in the integration lithium ion battery, there is lower lithium ion dissociation energy when preferably comprising fluorine-containing sulfimide moiety, to improve conductivity of the lithium ion in charge and discharge process, reduce the internal resistance of cell.In addition, the invention also provides the high integrated battery preparation methods of two kinds of simple production process, the electrode active material layers uniformity, it is with a wide range of applications in solid electrolyte field of lithium ion battery, especially high magnification, high-capacity dynamical solid electrolyte field of lithium ion battery.

Description

Solid electrolyte lithium ion battery and preparation method thereof of the integration without interface
Technical field
The invention belongs to lithium ion battery and its manufacturing fields, and in particular to a kind of solid electrolyte of the integration without interface Lithium ion battery and preparation method thereof.
Background technology
Currently, traditional lithium ion battery generally use is toxic and the liquid organic electrolyte easily revealed, thus there are one Fixed security risk and problem of environmental pollution.The poly-lithium battery that the nineties occurs uses the polymer of solid or gel state Electrolyte, thus have higher security and stability and more excellent environment friendly.In addition, polymer Li-ion battery is also With it is moulding flexibly, the advantages such as higher than energy, electrochemical stability window is wide, capacitance loss is few, volume utilization is high, be the following lithium The main direction of development of ion battery.
But compared with it can be thoroughly impregnated the liquid electrolyte of electrode plates, polymer dielectric has solidity Matter, conductibility of the lithium ion in solid electrolyte are far below liquid electrolyte;And polymer dielectric and electrode plates it Between there is a problem of that closeness of contact is not good enough.In addition, the passivating film due to solid electrolyte is stablized relatively, so if used The compatibility of solid electrolyte and electrode plates is poor will to be led to passivating film extension at any time and increases, to increase battery Internal resistance.Therefore, it is to be badly in need of solving in the development of solid electrolyte lithium battery applications to improve the compatibility between electrode material and electrolyte A key technical problem certainly.
For this technical bottleneck, researchers attempt to simplify the inside of lithium ion battery by constructing integral structure Structure improves the contact condition of different inter-modules, and then improves the compatibility between battery component, reduces the interior of lithium ion battery Resistance, to reach better energy-storage property.In the Chinese invention patent of Publication No. CN1219779A, researcher is to positive and negative electrode pole Polyelectrolyte solution is perfused in the active material layer containing active material and binder of piece, polymer dielectric is made to permeate Enter in anode and cathode active materials layer;Then solvent is evaporated, then the positive and negative electrode pole piece layer containing electrolyte is faced each other;Most Afterwards, the two poles of the earth pole piece is heated by external hot solvent and forms platypelloid type solid electrolyte polymer lithium battery together.This method is logical Infiltration of the electrolyte in electrode active material layers is crossed, the contact between electrolyte and active material is improved, reduces electricity Pond internal resistance has obtained the lithium ion battery of excellent contact performance and high electric discharge output.The China of Publication No. CN103413966A Patent of invention improves the compatibility of electrode material and anodic aluminium oxide membrane layer, and researcher will be with the nothing for infiltrating electrolyte Machine ceramic particle is sprayed on electrode plates, and lithium ion battery membrane electrode is obtained through drying, rolling.Such membrane electrode piece is realized Positive and negative electrode pole piece is integrated with isolation film, simplifies the structure of lithium ion battery, and gained lithium battery is shown better than passing The high-temperature stability of system structure lithium ion battery.
However, in order to further decrease the internal resistance of cell, the solid state electrolysis that contact performance is excellent, electric discharge output performance is high is obtained Matter lithium ion battery, it is still desirable to further increase between electrolyte and electrode active material it is compatible contact, make every effort to realization one Solid electrolyte lithium ion battery of the body without interface.
Invention content
The technical purpose of the present invention is the state of the art for above-mentioned solid electrolyte lithium ion battery, provides a kind of solid-state Electrolyte lithium-ion battery has the advantages that the internal resistance of cell is low, contact performance is excellent, specific discharge capacity is high, is a kind of one Change the solid electrolyte lithium ion battery without interface.
The technical solution adopted in the present invention is:Solid electrolyte lithium ion battery of the integration without interface, including anode Collector, the anode active material layer on plus plate current-collecting body, negative current collector, the anode active material layer on negative current collector, And solid electrolyte, the anode active material layer include positive electrode active materials, conductive agent and binder, the cathode Active material layer includes negative electrode active material, conductive agent and binder;It is characterized in that:In the binder and solid electrolyte Including identical material component, that is, including following situation:
(1) when the binder and solid electrolyte are homogenous material, binder material and solid state electrolysis material Expect identical;
(2) when the binder is combined material, and solid electrolyte is homogenous material, solid electrolyte material is viscous Tie one kind in agent material;
(3) when the binder is combined material, and solid electrolyte is combined material, binder and solid electrolyte In there are identical material components.
That is, the binders for electrodes in solid electrolyte lithium ion battery of the present invention is selected with solid electrolyte material Same material, or make in the two there are identical material component, between the electrode and electrolyte to be conducive to improve battery Compatibility improves conductivity of the lithium ion in charge and discharge process, reduces the internal resistance of cell, and can simplify battery and generate work Skill improves the uniformity of electrode material layer, therefore in solid electrolyte field of lithium ion battery, especially high magnification, large capacity It is with a wide range of applications in power solid electrolyte field of lithium ion battery.
In the present invention, the solid electrolyte material includes the polymeric material for having high ion-conductivity, high-adhesion Material is advisable.Preferably, the solid electrolyte is fluorine-containing sulfimide base polymeric material, or contain fluorine-containing sulphonyl The material of imido grpup polymers compositions contains fluorine-containing sulfonimide polymer group in the binder and solid electrolyte Point, that is, including following situation:
(1) when the binder material and solid electrolyte material are homogenous material, binder material and solid-state Electrolyte is same fluorine-containing sulfimide based polyalcohol;
(2) when the binder material is combined material, and solid electrolyte material is homogenous material, solid electrolyte Material is fluorine-containing sulfimide based polyalcohol, contains the same fluorine-containing sulfimide based polyalcohol component in binder material;
(3) when the binder material is combined material, and solid electrolyte material is also combined material, binder material There are identical fluorine-containing sulfimide based polyalcohol components in material and solid electrolyte material.
The fluorine-containing sulfimide base polymeric material is that main chain or side chain contain fluorine atom group simultaneously and sulphonyl is sub- The polymer and its inorganic nano composite material of amine groups, including poly- (the chloro- 3- oxa-s of 5- sulphonyl) perfluor sulfonyl amine lithium salts, side chain For the polyether-ether-ketone resin of fluorine-containing sulfimide base, the fluorine-containing sulfimide material such as fluorine-containing sulfimide based polyalcohol modified graphene The mixture of one or more of material.
The positive electrode active materials are unlimited, including oxide/lithium ferrite, lithium and cobalt oxides, lithium nickel oxide etc. contain lithium and mistake The compound-materials such as the oxide of metal, such as cobalt acid lithium, LiMn2O4, nickel ion doped are crossed, can also include sulfur-based positive electrode material.
The negative electrode active material is unlimited, including the carbon materials such as graphite, graphene, carbon nanotube and its composite wood Material, lithium metal, lithium-containing transition metal nitride, silica and silicon based composite material, sulfur-bearing inorganic compound etc..
The conductive agent material is unlimited, including acetylene black, Super P, carbon black etc..
The plus plate current-collecting body is unlimited, can be the materials such as aluminium foil.
The negative current collector is unlimited, can be the materials such as copper foil.
The method for preparing the above-mentioned integrated solid electrolyte lithium ion battery without interface the present invention also provides two kinds, A kind of middle preparation method is as shown in Figure 1, include the following steps:
(1) positive electrode active materials, conductive agent, binder and the first solvent are uniformly mixed, positive-active slurry is made; Negative electrode active material, conductive agent, binder and the second solvent are uniformly mixed, negative electrode active slurry is made;
(2) positive-active slurry is coated on plus plate current-collecting body surface, prepares anode pole piece 1;Negative electrode active slurry is applied It is overlying on negative current collector surface, prepares cathode pole piece 2;
(3) solid electrolyte material is dissolved in third solvent, electrolyte solution is made;
(4) electrolyte solution is respectively coated in anode pole piece surface and cathode pole piece surface, drying removes third solvent Dielectric film 3 is formed afterwards, anode pole piece is superimposed with cathode pole piece, keeps the two sides of coated electrolyte film 3 opposite, then uses mould Pressure forms it into one, and integrated lithium ion battery is made finally by subsequent handlings such as slice, winding, soldering polar ear, encapsulation.
First solvent is unlimited, including water, methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, N- crassitudes The mixture that one or more of ketone etc. material is mixed according to arbitrary proportion.
Second solvent is unlimited, including water, methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, N- crassitudes The mixture that one or more of ketone etc. material is mixed according to arbitrary proportion.
The third solvent is unlimited, including ethylene carbonate (EC), propene carbonate (CP), dimethyl carbonate (DMC), Methyl ethyl carbonate (EMC), diethyl carbonate (DEC), Y- fourths propyl ester (GBL), methyl formate (MF), methyl acetate (MVA), tetrahydrochysene It barks mutter (THF), l, the mixture of a kind of solvent or two kinds of solvents in 2- dimethoxy-ethanes (DME) etc..
In the step (2), painting method is unlimited, including the methods of spin coating, curtain coating, printing.
Preferably, the thickness of the anode pole piece is 10~300 μm ± 10 μm.
Preferably, the thickness of the cathode pole piece is 10~300 μm ± 10 μm.
Preferably, the electrolyte layer thickness is 50~200 μm.
Above-mentioned preparation method is simple, by infiltration of the electrolyte in electrode active material layers, improves electrolyte Compatibility between active material layer has obtained the lithium ion battery of height ratio capacity to reduce the internal resistance of cell.
But in above-mentioned preparation method, coating is susceptible in the coating of electrode activity particle and electrolyte coating procedure It is uneven, the bad problem of material.In addition, again by electrode plates and solid electrolyte membrane it is compressed together during Being susceptible to dielectric film linkage interface, there are gap or molding metabolies, so as to cause because of solid electrolyte material structure It is uneven and influence battery performance.
For this purpose, the present invention also provides another improved preparation method, spray coating method, as shown in Fig. 2, including following step Suddenly:
(1) positive electrode active materials, conductive agent, binder and the first solvent are uniformly mixed, positive-active slurry is made; Negative electrode active material, conductive agent, binder and the second solvent are uniformly mixed, negative electrode active slurry is made;
(2) positive-active slurry and negative electrode active slurry are sprayed on to the two sides of solid electrolyte membrane respectively;
(3) plus plate current-collecting body is arranged to the side for being coated with positive-active slurry in dielectric film, negative current collector is arranged It is coated with the side of negative electrode active slurry in dielectric film, is then suppressed by roll-in integral.
First solvent is unlimited, including water, methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, N- crassitudes The mixture that one or more of ketone etc. material is mixed according to arbitrary proportion.
Second solvent is unlimited, including water, methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, N- crassitudes The mixture that one or both of ketone etc. material is mixed according to arbitrary proportion.
It is sliced, wound in the above method, after step (3), soldering polar ear, the subsequent handlings such as encapsulation.
The above method has the following advantages that:
(1) using the two sides that positive and negative electrode active slurry is sprayed on to solid electrolyte membrane, positive and negative electrode work is substantially increased The uniformity of property material layer component, improves the conjugation of electrode active material and solid electrolyte;
(2) positive and negative electrode active slurry is sprayed using on the two sides of solid electrolyte membrane, it is then logical with positive and negative electrode collector Roll-in is crossed, is suppressed into one, therefore solid electrolyte material remains integrality, alleviates solid electrolyte material structure It is uneven and the problem of influence battery performance.
Description of the drawings
Fig. 1 is the schematic diagram that the integrated solid electrolyte lithium ion battery without interface of the present invention is prepared using cladding process;
Fig. 2 is the schematic diagram that the integrated solid electrolyte lithium ion battery without interface of the present invention is prepared using spray coating method.
Specific implementation mode
Below in conjunction with attached drawing embodiment, present invention is further described in detail, it should be pointed out that implementation as described below Example is intended to be convenient for the understanding of the present invention, and does not play any restriction effect to it.
Embodiment 1:
Integrated lithium ion battery is prepared using cladding process in the present embodiment.Integration is without interface solid electrolyte lithium ion Plus plate current-collecting body is aluminium foil in battery, and the anode active material layer on plus plate current-collecting body is by LiFePO4, Super P, and bond Agent forms;Negative current collector is copper foil, and the anode active material layer on negative current collector is by graphite, Super P and binder Composition;Solid electrolyte material and the polyether sulphone lithium salts that binder material is the fluorine-containing sulfimide base group of side chain, knot Structure formula is as follows:
The preparation method of solid electrolyte lithium ion battery of the integration without interface is as shown in Figure 1, including as follows
Step:
(1) binder solution processed
The polyether sulphone lithium salts that side chain is fluorine-containing sulfimide moiety is dissolved in N- methyl pyrroles at 50 DEG C with 5wt% concentration In pyrrolidone, the binder solution based on fluorine-containing sulfimide based polyalcohol lithium salts is prepared into after being sufficiently stirred 12 hours.
(2) positive and negative electrode pole piece processed
By the LiFePO of advance 80 parts of ground weight4, 10 parts of weight Super P and 10 parts of weight binder it is molten Liquid blended under agitation is prepared into positive-active slurry;Slurry is coated uniformly on 20 μm of aluminium foils again, the anode pole piece after coating is thick Degree control is at 200 μm ± 10 μm;After roll-in, obtained thickness is about 100 μm of anode pole pieces 1.
The preparation method of cathode pole piece is similar to preparing for anode pole piece, i.e., by the stone of advance 80 parts of ground weight The binder solution blended under agitation of ink, the Super P of 10 parts of weight and 10 parts of weight is prepared into negative electrode active slurry;Slurry is equal Even to be coated on 10 μm of copper foils, the cathode pole piece thickness overall thickness after coating is controlled at 180 μm ± 10 μm;After roll-in, system It is about 90 μm of cathode pole pieces 2 to obtain thickness.
(3) dielectric film processed
The polyether sulphone lithium salts that side chain is fluorine-containing sulfimide base group is dissolved in N- methyl pyrroles with the concentration of 25wt% In pyrrolidone, it is sufficiently stirred and obtains electrolyte solution for 24 hours;By electrolyte solution coated on positive and negative by way of tape casting On the pole piece active layer of pole;The overall thickness of electrode slice controls in 50~300 μ ms;The pole piece of electrolyte will have been coated in vacuum It is heated under environment, dry 72h, obtains dielectric film 3.Wherein, Electrolyte film thickness is optimal with 150 μm.
(4) dielectric film 3 of the positive and negative electrode pole piece after drying is faced each other into superposition, will be folded using the method for hot-rolling pressure Lamination thickness processed is the platypelloid type battery core less than 500 μm;Finally, pass through slice, winding, soldering polar ear, encapsulation, electrification, exhaust Etc. processes obtain integration without interface lithium ion battery.
Embodiment 2:
In the present embodiment, the preparation method and embodiment 1 of the integrated solid electrolyte lithium ion battery without interface are basic It is identical, except that solid electrolyte material and binder are poly- (the chloro- 3- oxa-s of 5- sulphonyl) perfluor sulfonyl amine polymer Lithium salts, the wherein thickness of solid electrolyte membrane are about still 150 μm.
Embodiment 3:
In the present embodiment, the preparation method and embodiment 2 of the integrated solid electrolyte lithium ion battery without interface are basic It is similar, except that binder material heterogeneous material but poly- (the chloro- 3- oxa-s of 5- sulphonyl) perfluor sulfonyl amine polymer lithium Salt presses 1 with Kynoar (PVDF):The mixture that 1 mass ratio mixes.
The preparation method of solid electrolyte lithium ion battery of the integration without interface is as shown in Figure 1, include the following steps:
(1) binder solution processed
Poly- (the chloro- 3- oxa-s of 5- sulphonyl) perfluor sulfonyl amine polymer lithium salts presses 1 with Kynoar (PVDF):1 quality Than mixing;Mixture is dissolved in 5wt% concentration in N-Methyl pyrrolidone at 50 DEG C, and base is prepared into after being sufficiently stirred 12 hours In the binder solution of fluorine-containing sulfimide based polyalcohol.
(2) positive and negative electrode pole piece processed
By the LiFePO of advance 80 parts of ground weight4, 10 parts of weight Super P and 10 parts of weight binder it is molten Liquid blended under agitation is prepared into positive-active slurry;Slurry is coated uniformly on 20 μm of aluminium foils again, the anode pole piece after coating is thick Degree control is at 200 μm ± 10 μm;After roll-in, obtained thickness is about 100 μm of anode pole pieces 1.
The preparation method of cathode pole piece is similar to preparing for anode pole piece, i.e., by the stone of advance 80 parts of ground weight The binder solution blended under agitation of ink, the Super P of 10 parts of weight and 10 parts of weight is prepared into negative electrode active slurry;Slurry is equal Even to be coated on 10 μm of copper foils, the cathode pole piece thickness overall thickness after coating is controlled at 180 μm ± 10 μm;After roll-in, system It is about 90 μm of cathode pole pieces 2 to obtain thickness.
(3) dielectric film processed
Poly- (the chloro- 3- oxa-s of 5- sulphonyl) perfluor sulfonyl amine polymer lithium salts is dissolved in N- methyl pyrroles with the concentration of 25wt% In pyrrolidone, it is sufficiently stirred and obtains electrolyte solution for 24 hours;By electrolyte solution coated on positive and negative by way of tape casting On the pole piece active layer of pole;The overall thickness of electrode slice controls in 50~300 μ ms;The pole piece of electrolyte will have been coated in vacuum It is heated under environment, dry 72h, obtains dielectric film 3.Wherein, Electrolyte film thickness is optimal with 150 μm;
(4) dielectric film 3 of the positive and negative electrode pole piece after drying is faced each other into superposition, will be folded using the method for hot-rolling pressure Lamination thickness processed is the platypelloid type battery core less than 500 μm;Finally, pass through slice, winding, soldering polar ear, encapsulation, electrification, exhaust Etc. processes obtain integration without interface lithium ion battery.
Embodiment 4:
In the present embodiment, the integrated solid electrolyte lithium ion battery without interface is prepared using spray coating method.Wherein, positive Collector is aluminium foil, and the anode active material layer on plus plate current-collecting body is by LiFePO4, Super P and binder composition;It is negative Pole collector is copper foil, and the anode active material layer on negative current collector is made of graphite, SuperP and binder;Solid-state Electrolyte and binder material are poly- (the chloro- 3- oxa-s of 5- sulphonyl) perfluor sulfonyl amine lithium salts.
The method of solid electrolyte lithium ion battery of the integration without interface is as shown in Fig. 2, include the following steps:
(1) dielectric film is prepared
Poly- (the chloro- 3- oxa-s of 5- sulphonyl) perfluor sulfonyl amine lithium salts is dissolved in N-Methyl pyrrolidone with the concentration of 25wt% In, it is sufficiently stirred and obtains the glutinous solution of electrolyte for 24 hours;Using film casting method, dielectric film 4 is made, the thickness of film is about 50-200 μ m;
(2) binder solution is prepared
Poly- (the chloro- 3- oxa-s of 5- sulphonyl) perfluor sulfonyl amine lithium salts is dissolved in N-Methyl pyrrolidone with 5wt% concentration, is filled It is prepared into the binder solution based on fluorine-containing sulfimide based polyalcohol after dividing stirring 12 hours;
(3) positive and negative electrode active slurry is prepared
By the LiFePO of advance 80 parts of ground weight4, 10 parts of weight Super P and 10 parts of weight binder it is molten Liquid blended under agitation is prepared into positive-active slurry 5;The preparation method of cathode pole piece is similar to preparing for anode pole piece, i.e., will be advance The graphite of 80 parts of ground weight, the Super P of 10 parts of weight and the binder solution blended under agitation of 10 parts of weight are prepared into Negative electrode active slurry 6;
(4) active slurry sprays
Positive and negative electrode active slurry 5,6 is sprayed to the two sides of dielectric film 4 respectively, forms three-layer sandwich film layer structure;It will The dielectric film coating for being coated with positive-active slurry corresponds to plus plate current-collecting body 7- aluminium foils, is coated with the dielectric film of negative electrode active slurry Coating corresponds to negative current collector 8- copper foils, forces together in roll squeezer upper mold with dielectric film;Finally, pass through slice, winding, weldering It connects the processes such as lug, encapsulation, electrification, exhaust and obtains integration without interface lithium ion battery.
Embodiment 5:
In the present embodiment, the preparation method and embodiment 4 of the integrated solid electrolyte lithium ion battery without interface are basic It is similar, except that binder material heterogeneous material but poly- (the chloro- 3- oxa-s of 5- sulphonyl) perfluor sulfonyl amine polymer lithium Salt presses 1 with Kynoar (PVDF):The mixture that 1 mass ratio mixes.
The method of solid electrolyte lithium ion battery of the integration without interface is as shown in Fig. 2, include the following steps:
(1) dielectric film processed
Poly- (the chloro- 3- oxa-s of 5- sulphonyl) perfluor sulfonyl amine lithium salts is dissolved in N-Methyl pyrrolidone with the concentration of 25wt% In, it is sufficiently stirred for 24 hours, obtains electrolyte and stick solution;Using film casting method, dielectric film 4 is made, the thickness of film is about 50-200 μm。
(2) binder solution is prepared:
Poly- (the chloro- 3- oxa-s of 5- sulphonyl) perfluor sulfonyl amine lithium salts and Kynoar (PVDF) are pressed 1:1 mass ratio is mixed It closes;Mixture is dissolved in 5wt% concentration in N-Methyl pyrrolidone, is prepared into after being sufficiently stirred 12 hours based on fluorine-containing sulphonyl Asia The binder solution of amine based polymer;
(3) positive and negative electrode active slurry is prepared
By the LiFePO of advance 80 parts of ground weight4, 10 parts of weight Super P and 10 parts of weight binder it is molten Liquid blended under agitation is prepared into positive-active slurry 5;The preparation method of cathode pole piece is similar to preparing for anode pole piece, i.e., will be advance The graphite of 80 parts of ground weight, the Super P of 10 parts of weight and the binder solution blended under agitation of 10 parts of weight are prepared into Negative electrode active slurry 6;
(4) active slurry sprays:
Positive and negative electrode active slurry is sprayed to the two sides of dielectric film respectively, forms three-layer sandwich film layer structure;It will be coated with The dielectric film coating of positive-active slurry corresponds to plus plate current-collecting body 7- aluminium foils, is coated with the dielectric film coating of negative electrode active slurry Corresponding negative current collector 8- copper foils, force together with dielectric film in roll squeezer upper mold;Finally, pass through slice, winding, welding pole The processes such as ear, encapsulation, electrification, exhaust obtain integration without interface lithium ion battery.
Embodiment 6:
In the present embodiment, the preparation method and embodiment 4 of the integrated solid electrolyte lithium ion battery without interface are basic It is similar, except that solid electrolyte material and the polyethers ether that binder material is that side chain is fluorine-containing sulfimide base group Ketone resin material.
The method of solid electrolyte lithium ion battery of the integration without interface is as shown in Fig. 2, include the following steps:
(1) dielectric film processed
The polyether-ether-ketone resin that side chain is fluorine-containing sulfimide base group is dissolved in N- methyl pyrroles with the concentration of 30wt% In pyrrolidone, it is sufficiently stirred and obtains the glutinous solution of electrolyte for 24 hours;Using film casting method, dielectric film 4 is made, the thickness of film is about 50-200μm;
(2) binder solution is prepared
The polyether-ether-ketone resin that side chain is fluorine-containing sulfimide base group is pressed 1 with Kynoar (PVDF):1 quality Than mixing;Mixture is dissolved in 5wt% concentration in N-Methyl pyrrolidone at 50 DEG C, and base is prepared into after being sufficiently stirred 12 hours In the binder solution of fluorine-containing sulfimide based polyalcohol;
(3) positive and negative electrode active slurry is prepared
The LiFePO of advance 80 parts of ground weight4, 10 parts of weight Super P and 10 parts of weight binder solution Blended under agitation is prepared into positive-active slurry 5;The preparation method of cathode pole piece is similar to preparing for anode pole piece, i.e., will grind in advance The binder solution blended under agitation of the graphite of 80 parts of honed weight, the Super P of 10 parts of weight and 10 parts of weight is prepared into negative Pole active slurry 6;
(4) active slurry sprays
Anode and cathode active materials slurry is sprayed to the two sides of dielectric film respectively, forms three-layer sandwich film layer structure;It will The dielectric film coating for being coated with positive electrode active materials corresponds to plus plate current-collecting body 7- aluminium foils, is coated with the dielectric film of negative electrode active material Coating corresponds to negative current collector 8- copper foils, forces together in roll squeezer upper mold with dielectric film;Finally, pass through slice, winding, weldering It connects the processes such as lug, encapsulation, electrification, exhaust and obtains integration without interface lithium ion battery.
Embodiment 7:
In the present embodiment, the preparation method and embodiment 4 of the integrated solid electrolyte lithium ion battery without interface are basic It is similar, except that solid electrolyte membrane solid electrolyte material is poly- (the chloro- 3- oxa-s of 5- sulphonyl) perfluor sulfonyl amine lithium salts Surface modified graphite alkene composite material is with poly- (the chloro- 3- oxa-s of 5- sulphonyl) perfluor sulfonyl amine lithium salts with 5:It is mixed made of 95 blendings Object, binder material are that poly- (the chloro- 3- oxa-s of 5- sulphonyl) perfluor sulfonyl amine lithium salts presses 1 with Kynoar (PVDF):1 quality Than the mixture mixed.
The method of solid electrolyte lithium ion battery of the integration without interface is as shown in Fig. 2, include the following steps:
(1) dielectric film processed
By poly- (the chloro- 3- oxa-s of 5- sulphonyl) perfluor sulfonyl amine lithium salts surface modified graphite alkene composite material and poly- (5- sulphonyl Chloro- 3- oxa-s) perfluor sulfonyl amine lithium salts is with 5:95 are blended, and are dissolved with the concentration of solid mixture matter total mass fraction 25wt% In N-Methyl pyrrolidone, it is sufficiently stirred and obtains the glutinous solution of electrolyte for 24 hours;Using film casting method, dielectric film 4, film is made Thickness be about 50-200 μm;
(2) binder solution is prepared
Poly- (the chloro- 3- oxa-s of 5- sulphonyl) perfluor sulfonyl amine lithium salts and Kynoar (PVDF) are pressed 1:1 mass ratio is mixed It closes;Mixture is dissolved in 5wt% concentration in N-Methyl pyrrolidone at 50 DEG C, is prepared into after being sufficiently stirred 12 hours and is based on containing The binder solution of fluorine sulfimide based polyalcohol;
(3) positive and negative electrode active slurry is prepared
By the LiFePO of advance 80 parts of ground weight4, 10 parts of weight Super P and 10 parts of weight binder it is molten Liquid blended under agitation is prepared into positive-active slurry 5;The preparation method of cathode pole piece is similar to preparing for anode pole piece, i.e., will be advance Poly- (the chloro- 3- oxa-s of 5- sulphonyl) the perfluor sulfonyl amine lithium salts surface modified graphite alkene of 80 parts of ground weight, 10 parts of weight The binder solution blended under agitation of Super P and 10 parts of weight is prepared into negative electrode active slurry 6;
(4) active slurry sprays
Positive and negative electrode active slurry is sprayed to the two sides of dielectric film respectively, forms three-layer sandwich film layer structure;It will be coated with The dielectric film coating of positive-active slurry corresponds to plus plate current-collecting body 7- aluminium foils, is coated with the dielectric film coating of negative electrode active material Corresponding negative current collector 8- copper foils force together with dielectric film in roll squeezer upper mold;Finally, pass through slice, winding, welding pole The processes such as ear, encapsulation, electrification, exhaust obtain integration without interface lithium ion battery.

Claims (8)

1. the preparation method of the integrated solid electrolyte lithium ion battery without interface, the solid electrolyte lithium ion battery packet Include plus plate current-collecting body, anode active material layer, negative current collector, anode active material layer, solid electrolyte membrane;The anode Active material layer includes positive electrode active materials, conductive agent and binder;The anode active material layer includes negative electrode active material Material, conductive agent and binder;It is characterized in that:The binder polymerize with solid electrolyte comprising fluorine-containing sulfimide of the same race Object component;
The fluorine-containing sulfonimide polymer is that the straight chain polymer of fluorine-containing sulfimide base or fluorine-containing sulfimide base gather Close the composite material of object surface-modified inorganic nano particle;
The preparation method includes the following steps:
(1) positive electrode active materials, conductive agent, binder and the first solvent are uniformly mixed, positive-active slurry is made;It will bear Pole active material, conductive agent, binder and the second solvent are uniformly mixed, and negative electrode active slurry is made;
(2) positive-active slurry is coated on plus plate current-collecting body surface, prepares anode pole piece;Negative electrode active slurry is coated on negative Pole collection liquid surface, prepares cathode pole piece;
(3) solid electrolyte material is dissolved in third solvent, electrolyte solution is made;
(4) electrolyte solution is respectively coated in anode pole piece surface and cathode pole piece surface, drying removes shape after third solvent At dielectric film, anode pole piece is superimposed with cathode pole piece, keeps the two sides of coated electrolyte film opposite, then hot-rolling pressure, it will be electric Pole layer and dielectric film consolidation.
2. the preparation method of solid electrolyte lithium ion battery of the integration without interface as described in claim 1, it is characterized in that: The fluorine-containing sulfonimide polymer is poly- (the chloro- 3- oxa-s of 5- sulphonyl) perfluor sulfonyl amine lithium salts, and fluorine-containing sulfimide base is poly- One or both of polymer modified graphene.
3. the preparation method of solid electrolyte lithium ion battery of the integration without interface as described in claim 1, it is characterized in that: The positive electrode active materials include the mixing material of one or more of cobalt acid lithium, LiMn2O4, nickel ion doped.
4. the preparation method of solid electrolyte lithium ion battery of the integration without interface as described in claim 1, it is characterized in that: The negative electrode active material includes that graphite, graphene, carbon nanotube, lithium-containing transition metal nitride, silica, silicon substrate are compound The mixing material of one or more of material, sulfur-bearing inorganic compound.
5. the preparation method of solid electrolyte lithium ion battery of the integration without interface as described in claim 1, it is characterized in that: The conductive agent includes the mixing material of one or more of acetylene black, Super P, carbon black.
6. the preparation method of solid electrolyte lithium ion battery of the integration without interface as described in claim 1, it is characterized in that: First solvent include one kind in water, methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, N-Methyl pyrrolidone or Two or more mixtures;
Second solvent includes one in water, methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, N-Methyl pyrrolidone Kind material or two or more mixtures;
The third solvent includes ethylene carbonate (EC), propene carbonate (CP), dimethyl carbonate (DMC), methyl ethyl carbonate Ester (EMC), diethyl carbonate (DEC), Y- fourths propyl ester (GBL), methyl formate (MF), methyl acetate (MVA), tetrahydrochysene bark and mutter (THF), a kind of solvent in l, 2- dimethoxy-ethane (DME) or two or more mixtures.
7. the preparation method of the integrated solid electrolyte lithium ion battery without interface, it is characterized in that:The solid electrolyte lithium Ion battery includes plus plate current-collecting body, anode active material layer, negative current collector, anode active material layer, solid electrolyte membrane; The anode active material layer includes positive electrode active materials, conductive agent and binder;The anode active material layer includes Negative electrode active material, conductive agent and binder;It is characterized in that:Include fluorine-containing sulphur of the same race in the binder and solid electrolyte Imide polymer component;
The fluorine-containing sulfonimide polymer is that the straight chain polymer of fluorine-containing sulfimide base or fluorine-containing sulfimide base gather Close the composite material of object surface-modified inorganic nano particle;
The preparation method includes the following steps:
(1) positive electrode active materials, conductive agent, binder and the first solvent are uniformly mixed, positive-active slurry is made;It will bear Pole active material, conductive agent, binder and the second solvent are uniformly mixed, and negative electrode active slurry is made;
(2) positive-active slurry and negative electrode active slurry are sprayed on to the two sides of solid electrolyte membrane respectively;
(3) plus plate current-collecting body is arranged to the side for being coated with positive-active slurry in dielectric film, negative current collector 8 is arranged in electricity Solution plasma membrane is coated with the side of negative electrode active slurry, then hot-rolling pressure, and electrode layer and dielectric film compacting are integrated.
8. the preparation method of solid electrolyte lithium ion battery of the integration without interface as claimed in claim 7, it is characterized in that: First solvent include one kind in water, methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, N-Methyl pyrrolidone or Two or more arbitrary proportion mixtures;
Second solvent includes one in water, methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, N-Methyl pyrrolidone Kind or two or more arbitrary proportion mixtures.
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