CN105006592A - Gel electrolyte lithium ion battery with composite electrode and preparation method thereof - Google Patents
Gel electrolyte lithium ion battery with composite electrode and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a gel electrolyte lithium ion battery with a composite electrode and a preparation method thereof. The gel electrolyte lithium ion battery with the composite electrode comprises a battery shell with a positive terminal and a negative terminal and a battery monomer composed of a positive and negative unit, the positive and negative unit is formed by overlapping a negative current collector, a composite negative layer, a gel electrolyte layer, a composite positive layer and a positive current collector, the composite positive layer and the composite negative layer are formed by uniformly mixing positive material powder and negative material powder with positive and negative gel electrolyte respectively, the positive current collector is electrically connected with the positive terminal, and the negative current collector is electrically connected with the negative terminal. Compared with the prior art, according to the gel electrolyte lithium ion battery with the composite electrode and the preparation method thereof, liquid state electrolyte is replaced by the gel electrolyte, better safety is achieved, the gel electrolyte and solid electrode materials form the composite electrode, the transportation rate of lithium ions in the electrodes is improved, the multiplying power character and energy storage density of the lithium ion battery and the effective utilization of the electrode materials are improved, and the battery only needs one positive and negative unit to complete various power supply tasks.
Description
Technical field
The present invention relates to electric energy technical field, particularly relate to a kind of gel electrolyte lithium ion battery and preparation method thereof.
Background technology
Since nineteen ninety, Sony corporation of Japan released first commercially produced product, lithium ion battery has become one of of paramount importance electric energy memory technology.In recent years, the emerging application form being the electric energy memory of representative with electrical vehicular power power supply, adjustable energy storage etc., proposes new requirement to the energy storage density of lithium ion battery, multiplying power property and fail safe.
The traditional lithium ion battery technology being widely used in commercially produced product at present above-mentioned several in all there is the intrinsic limitation being difficult to overcome.First, conventional lithium ion battery technology relies on liquid electrolyte between both positive and negative polarity, forms lithium ion transport path, but the chemical characteristics such as liquid electrolyte easily decomposes, inflammable and explosive bring serious potential safety hazard to conventional lithium ion battery.Secondly, the materials such as cobalt acid lithium, LiMn2O4, LiFePO4, graphite, silicon are used to make the solid state electrode of battery in conventional lithium ion battery technology, in the solid state electrode that lithium ion is formed at above-mentioned material, transmission rate is lower, causes the multiplying power property of lithium ion battery cannot meet requirement for fast charging and discharging in emerging application.And, be limited in solid electrolyte and obtain lithium ion transport speed, often through using thinner electrode (general 50 to 120 μm) to shorten the transport path of lithium ion, the mode such as adhesive, conductive adjuvant that is mixed in solid state electrode to obtain good multiplying power property in battery cell in conventional lithium ion battery technology, but, said method makes the non-energy storage section such as collector, adjuvant in lithium ion battery, occupy appreciable weight ratio, causes the energy storage density of lithium ion battery to be difficult to improve.In addition, the lithium ion transport speed that solid state electrode is lower makes some electrode materials possibility and performance energy storage effect not yet in effect.
The schematic diagram of traditional lithium ion battery as shown in Figure 1, be limited to solid-state positive pole 102, the ion guide passband of solid-state negative pole 104 and conductivity, the thickness of solid-state positive pole 102, solid-state negative pole 104 is generally 50 μm to 120 μm, is provided with the electrolyte 103 covering barrier film between solid-state positive pole 102 and solid-state negative pole 104.In order to obtain larger battery cell capacity, lamination process shown in general employing accompanying drawing 1, often comprise tens even tens of traditional plus plate current-collecting bodies 101 and traditional negative current collectors 105 in a battery cell, this is very big to the negative effect of battery energy storage density.
At present; in order to break through the limitation of existing lithium ion battery technology; researcher in this field has devised the multiple new type lithium ion battery having new construction or use new material; and new construction or new diseases often relate to the new technology of supporting exploitation; lithium ion battery is as a kind of electric energy product; if the large-scale production manufacture that productive rate, cost are controlled cannot be realized; its real value will be had a greatly reduced quality; but a lot of new technology manufactures the reasons such as equipment because technology stability is not good enough, lack industrialization, is difficult to the industrialized manufacture realizing amplification scale.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of use safety, multiplying power property is high, electrode material utilization is high, energy storage density is large, large-scale production cost is low and gel electrolyte lithium ion battery with combination electrode that productive rate is high and preparation method thereof.
The technical scheme that the present invention solves the problems of the technologies described above is as follows:
A kind of gel electrolyte lithium ion battery with combination electrode, it comprises with positive terminal, the battery case of negative terminal and the battery cell be encapsulated in described battery case, described battery cell comprises a both positive and negative polarity unit, described both positive and negative polarity unit is layer structure, and successively by negative current collector, composite negative pole layer, gel electrolyte layer, anode composite layer and plus plate current-collecting body are formed by stacking, described anode composite layer is formed by positive electrode powder and positive pole gel electrolyte Homogeneous phase mixing, described gel electrolyte layer is the gel layer be made up of gel electrolyte, described composite negative pole layer is formed by negative material powder and negative pole gel electrolyte Homogeneous phase mixing, described plus plate current-collecting body is electrically connected with the positive terminal on described battery case, described negative current collector is electrically connected with the negative terminal on described battery case.
Compared with prior art, the invention has the beneficial effects as follows:
Product of the present invention uses gel electrolyte to substitute traditional liquid electrolyte, without the need to using barrier film, avoid the problems such as the decomposition of liquid electrolyte, volatilization, burning and blast, and effectively suppress the growth of lithium metal dendritic crystal, significantly improve the fail safe of lithium ion battery; Simultaneously, gel electrolyte and solid state electrode material is used to form combination electrode, form in solid state electrode inside the path being convenient to lithium ion transport with gel electrolyte, improve lithium ion and transport speed in electrode interior, and increase electrode material and electrolytical contact area, improve the probability of the lithium ion generation electrochemical reaction in electrode material and electrolyte, thus substantially increase the multiplying power property of lithium ion battery; Have in the combination electrode of higher li ion transmission performance, electrode material effective rate of utilization is high, make can use thicker electrode in lithium ion battery, decrease the use of collector, and avoid the use of adhesive, conductive adjuvant, greatly reduce the ratio of non-energy storage active material in lithium ion battery, improve the energy storage density of lithium ion battery, only need the battery comprising a both positive and negative polarity unit can complete various power supply task; In addition, Total Product of the present invention has flexibility, still can normally work under bending, rolled state.
On the basis of technique scheme, the present invention can also do following improvement.
As a kind of preferred implementation of the present invention, the thickness of described anode composite layer, described composite negative pole layer is 100-10000 μm.
The beneficial effect of above-mentioned preferred version is adopted to be:
Because just, negative current collector only plays electronics conduction in the battery, can not storage power, their quantity is fewer, battery energy storage density is higher, battery energy storage capacity is larger, and the gel electrolyte in the present invention in combination electrode significantly improves the transport property of lithium ion in electrode, make the thickness of combination electrode can obtain preferably battery multiplying power property and electrode material effective rate of utilization in the scope of 100-10000 μm, it is very thick that the thickness of combination electrode can do, thus just greatly reduce, the usage quantity of negative current collector, improve battery energy storage density and stored energy capacitance, such battery only needs a both positive and negative polarity unit can complete various power supply task.
As another kind of preferred implementation of the present invention, described plus plate current-collecting body employing thickness is the aluminium foil of 10-100 μm, and described negative current collector employing thickness is the Copper Foil of 8-100 μm, and the thickness of described gel electrolyte layer is 1-200 μm.
The beneficial effect of above-mentioned preferred version is adopted to be:
Thickness is adopted to be that the aluminium foil of 10-100 μm is as plus plate current-collecting body, thickness is adopted to be that the Copper Foil of 8-100 μm is as negative current collector, and thickness is that the gel electrolyte layer of 1-200 μm can either be cost-saving, can be good at again the normal use meeting battery, transport for inside battery lithium ion provides better condition, makes the battery only comprising a both positive and negative polarity unit better can complete various power supply task.
As another kind of preferred implementation of the present invention, described positive electrode powder is that one is selected from cobalt acid lithium, lithium iron phosphate, spinel structure LiMn2O4, the powder of the anode material for lithium-ion batteries of nickel-cobalt-manganternary ternary anode material or nickel cobalt aluminium tertiary cathode material, described negative material powder is that one is selected from carbon negative pole material, silicon based anode material, lithium an-ode material, alloy type negative material, the powder of the lithium ion battery negative material in transition metal oxide negative material, described positive electrode powder, the particle diameter of described negative material powder is micron order, submicron order or nanoscale.
The beneficial effect of above-mentioned preferred version is adopted to be:
The charge and discharge process of lithium ion battery is exactly embedding and the deintercalation process of lithium ion; The positive electrode used in traditional lithium-ion battery or can take LiFePO4 as the polyanionic structure positive electrode etc. of representative for cobalt acid lithium, spinel structure LiMn2O4, nickel-cobalt-manganternary ternary anode material, nickel cobalt aluminium tertiary cathode material, the negative material in traditional lithium-ion battery can be lithium an-ode material, carbon based negative electrodes, tin base cathode material, silicon-based anode, with ashbury metal be representative alloy material of cathode or with molybdenum dioxide, tungsten dioxide, nickel oxide, manganese dioxide transition metal oxide negative material etc.
Anode composite layer, composite negative pole layer is by the positive electrode used in traditional lithium-ion battery, the powder of negative material and gel electrolyte Homogeneous phase mixing, described positive electrode powder, the particle diameter of described negative material powder is micron order, submicron order or nanoscale, positive electrode can be ensured, the powder of negative material and gel electrolyte are mixed to get more even, the easier path being convenient to lithium ion transport in the formation of combination electrode inside, improve lithium ion and transport speed in electrode interior, increase electrode material and electrolytical contact area, improve the probability of the lithium ion generation electrochemical reaction in electrode material and electrolyte, the multiplying power property of larger lithium ion battery and the effective rate of utilization of electrode material.
The inside of anode composite layer, composite negative pole layer, gel electrolyte and positive electrode powder, the mixing of negative material powder can be using gel electrolyte as continuous phase, and positive electrode powder, negative material powder be distributed in wherein respectively; Also can be positive electrode powder, negative material powder respectively as continuous phase, and gel electrolyte is distributed in wherein; Even if positive electrode powder, negative material powder and positive and negative electrode gel electrolyte do not possess significant continuous phase/discontinuous phase feature, anode composite, composite negative pole also can embody its beneficial effect, make the battery only comprising a both positive and negative polarity unit better can complete various power supply task, if and the inside of anode composite layer, composite negative pole layer take gel electrolyte as continuous phase, and the path degree of crook that gel electrolyte is formed is lower, best results.
As another kind of preferred implementation of the present invention, described gel electrolyte comprise gel electrolyte solvent, polymer, lithium salts, lithium salts solvent and one or more be selected from the additive of plasticizer, surfactant, flame-retardant additive, antioxidant, conductive additive, film for additive, anti-overcharge additive; Described positive pole gel electrolyte comprise gel electrolyte solvent, polymer for the formation of described gel electrolyte skeleton structure, lithium salts, lithium salts solvent and one or more be selected from the additive of plasticizer, surfactant, flame-retardant additive, antioxidant, conductive additive, film for additive, anti-overcharge additive; Described negative pole gel electrolyte comprise gel electrolyte solvent, polymer for the formation of described gel electrolyte skeleton structure, lithium salts, lithium salts solvent and one or more be selected from the additive of plasticizer, surfactant, flame-retardant additive, antioxidant, conductive additive, film for additive, anti-overcharge additive.
The beneficial effect of above-mentioned preferred version is adopted to be:
Gel electrolyte take polymer as skeleton, electrolyte and other material are filled in wherein, overall in gel state, ionic conductivity is good, stability is strong, plasticizer is added in gel electrolyte, surfactant, flame-retardant additive, antioxidant, conductive additive, film for additive, the optimization additive that anti-overcharge additive etc. are corresponding, better can optimize the film forming characteristics of gel electrolyte, be separated characteristic, ionic conductivity, thermal stability, chemical stability etc., make the battery only comprising a both positive and negative polarity unit better can complete various power supply task.
As another kind of preferred implementation of the present invention, described polymer is selected from polyoxyethylene, polymethyl acrylate, polyacrylonitrile, polymethyl methacrylate, polyvinyl chloride, polyvinyl acetate, Kynoar or Kynoar for one or more; The material of hexafluoropropylene copolymer, described gel electrolyte solvent is acetone, oxolane, dimethyl formamide or pyridine, described lithium salts is lithium hexafluoro phosphate, hexafluoroarsenate lithium, LiBF4, oxalic acid difluoro boric acid, lithium perchlorate, trifluoromethyl sulfonic acid lithium or two trifluoromethanesulfonimide lithium, and described lithium salts solvent is that one or more are selected from the solvent of propene carbonate, ethylene carbonate, diethyl carbonate, methyl ethyl carbonate, dibutyl phthalate, succinonitrile, dimethyl carbonate.
The beneficial effect of above-mentioned preferred version is adopted to be:
The gel electrolyte ion guide passband prepared of above-mentioned polymer, gel electrolyte solvent, lithium salts, lithium salts solvent compared with high, electrochemical stability window large, Heat stability is good; and and the various coating process applicability such as slot coated, scraper for coating, silk screen printing good; be applicable to large-scale production, wherein gel electrolyte solvent polarity is moderate, better to the general dissolubility of various material.
As another kind of preferred implementation of the present invention, described battery cell comprises multiple described both positive and negative polarity unit, and adjacent described both positive and negative polarity unit polarity is contrary and be superimposed together by a shared plus plate current-collecting body or negative current collector.
The beneficial effect of above-mentioned preferred version is adopted to be: a battery cell arranges multiple both positive and negative polarity unit, only all plus plate current-collecting bodies need be electrically connected, all negative current collectors are electrically connected, them are allowed to be electrically connected with the positive terminal on battery case, negative terminal respectively again, just can obtain larger battery capacity, meet the needs of special circumstances.
Have a preparation method for the gel electrolyte lithium ion battery of combination electrode as above, it comprises the following steps:
A, preparation gel electrolyte, composite positive pole and composite negative pole material:
Prepare gel electrolyte, positive pole gel electrolyte, negative pole gel electrolyte respectively, positive electrode powder is added in positive pole gel electrolyte, and mix, obtain composite positive pole, negative material powder is added again in negative pole gel electrolyte, and mix, obtain composite negative pole material;
B, coating composite negative pole material and gel electrolyte:
Get negative current collector, by the composite negative pole material of slot coated technique described in coated on one side one deck of negative current collector, then be coated with the gel electrolyte described in one deck thereon by slot coated technique, namely obtain negative pole unit;
C, coating composite positive pole and gel electrolyte:
Get plus plate current-collecting body, by the composite positive pole of slot coated technique described in coated on one side one deck of plus plate current-collecting body, then be coated with the gel electrolyte described in one deck thereon by slot coated technique, namely obtain positive pole unit;
D, assembling and encapsulation:
Described positive pole unit is coated with the one side that the one side of described gel electrolyte and described negative pole unit be coated with described gel electrolyte to fit tightly, carry out lamination assembling, obtain a both positive and negative polarity unit, namely the battery cell comprising a both positive and negative polarity unit is obtained, finally battery cell is encapsulated into positive terminal, the battery case of negative terminal, described plus plate current-collecting body is electrically connected with the positive terminal on described battery case, described negative current collector is electrically connected with the negative terminal on described battery case, namely the described gel electrolyte lithium ion battery with combination electrode is obtained.
Compared with prior art, the invention has the beneficial effects as follows:
The inventive method with slot coated (Slot Die Coating) technique for core, processing step is simple, be convenient to realize Industry Promotion application, the positive pole unit of gained and the surface of negative pole unit all scribble gel electrolyte, during lamination assembling, homogeneous material is easily at contact interface place good contact, be conducive to forming good ion transport passage, gel electrolyte is adopted to substitute traditional liquid electrolyte, without the need to using barrier film, avoid the decomposition of liquid electrolyte, volatilization, the problems such as burning and blast, and effectively suppress the growth of lithium metal dendritic crystal, the remarkable fail safe improving lithium ion battery, simultaneously, gel electrolyte and solid state electrode material is used to form combination electrode, form in solid state electrode inside the path being convenient to lithium ion transport with gel electrolyte, improve lithium ion and transport speed in electrode interior, and increase electrode material and electrolytical contact area, improve the probability of the lithium ion generation electrochemical reaction in electrode material and electrolyte, thus substantially increase the multiplying power property of lithium ion battery, have in the combination electrode of higher li ion transmission performance, electrode material effective rate of utilization is high, make can use thicker electrode in lithium ion battery, decrease the use of collector, and avoid the use of adhesive, conductive adjuvant, greatly reduce the ratio of non-energy storage active material in lithium ion battery, improve the energy storage density of lithium ion battery.
On the basis of technique scheme, the present invention can also do following improvement.
As another kind of preferred implementation of the present invention, in step, gel electrolyte, composite positive pole and composite negative pole material is prepared under the condition of exclusion of water and oxygen, ultrasonic process or mechanical agitation mode is adopted to carry out married operation, in step D, first use the gel electrolyte of infiltrate to described positive pole unit and described negative pole cell surface to infiltrate, then carry out lamination assembling.
In the present invention, infiltrate can use gel electrolyte solvent, lithium salts solvent, lithium salt solution etc.
The beneficial effect of above-mentioned preferred version is adopted to be:
Under the condition of exclusion of water and oxygen, prepare gel electrolyte, the gel electrolyte character obtained is more stable, and action effect is better; Adopt ultrasonic process or mechanical agitation mode to carry out married operation, can promote that positive electrode powder, negative material powder and gel electrolyte dissolve each other and spread, ensure the mixing that each component is full and uniform; First use the gel electrolyte of infiltrate to its surface to infiltrate, after being conducive to lamination, both interfaces form good contact.
As another kind of preferred implementation of the present invention, in stepb, after obtaining described negative pole unit, separately get negative current collector, the composite negative pole material described in one deck is coated with respectively on the two sides of the described negative current collector separately got by slot coated technique, be coated with the gel electrolyte described in one deck respectively thereon by slot coated technique again, namely obtain the negative pole module of double spread;
In step C, after obtaining described positive pole unit, separately get plus plate current-collecting body, the composite positive pole described in one deck is coated with respectively on the two sides of the described plus plate current-collecting body separately got by slot coated technique, be coated with the gel electrolyte described in one deck respectively thereon by slot coated technique again, namely obtain the positive pole module of double spread;
In step D, first hocket one or more described negative pole module and one or more described positive pole module lamination assembling, then lamination assembling is carried out with the described positive pole unit matched or described negative pole unit respectively in their both sides, namely obtain comprising multiple both positive and negative polarity element cell monomer.
The beneficial effect of above-mentioned preferred version is adopted to be:
Multiple both positive and negative polarity unit is set in a battery cell, larger battery capacity can be obtained, meet the needs of special circumstances.
Accompanying drawing explanation
Fig. 1 is the structural representation of conventional lithium ion battery;
Fig. 2 is the structural representation of product of the present invention when comprising a both positive and negative polarity unit;
Fig. 3 is the structural representation of product of the present invention when comprising multiple both positive and negative polarity unit;
In accompanying drawing, the list of parts representated by each label is as follows:
101, traditional plus plate current-collecting body, 102, solid-state positive pole, 103, cover the electrolyte of barrier film, 104, solid-state negative pole, 105, traditional negative current collector, 200, both positive and negative polarity unit, 201, negative current collector, 202, composite negative pole layer, 203, anode composite layer, 204, plus plate current-collecting body, 205, gel electrolyte layer, 206, battery cell, 207, positive pole unit, 208, negative pole unit, 209, positive pole module, 210, negative pole module.
Embodiment
Be described principle of the present invention and feature below in conjunction with accompanying drawing, example, only for explaining the present invention, is not intended to limit scope of the present invention.
Embodiment 1
As shown in Figure 2, a kind of gel electrolyte lithium ion battery with combination electrode, it comprises battery case with positive terminal, negative terminal and the battery cell 206 that is encapsulated in described battery case, described battery cell 206 comprises a both positive and negative polarity unit 200, described both positive and negative polarity unit 200 is layer structure, and be formed by stacking by negative current collector 201, composite negative pole layer 202, gel electrolyte layer 205, anode composite layer 203 and plus plate current-collecting body 204 successively, described plus plate current-collecting body 204 can adopt thickness to be 10, the aluminium foil of 100 μm, described negative current collector 201 can adopt thickness to be the Copper Foil of 8-100 μm, described anode composite layer 203 is formed by positive electrode powder and positive pole gel electrolyte Homogeneous phase mixing, thickness is preferably 100-10000 μm, described gel electrolyte layer 205 is the gel layers be made up of gel electrolyte, thickness is preferably 1-200 μm, described composite negative pole layer 202 is formed by negative material powder and negative pole gel electrolyte Homogeneous phase mixing, thickness can be preferably 100-10000 μm, described plus plate current-collecting body 204 is electrically connected with the positive terminal on described battery case, described negative current collector 201 is electrically connected with the negative terminal on described battery case,
Described positive electrode powder can select the powder of the traditional lithium-ion battery positive electrodes such as cobalt acid lithium, lithium iron phosphate, spinel structure LiMn2O4, nickel-cobalt-manganternary ternary anode material or nickel cobalt aluminium tertiary cathode material;
Described negative material powder can select carbon negative pole material, silicon based anode material, lithium an-ode material, the powder of the lithium ion battery negative material in alloy type negative pole or transition metal oxide negative material, carbon negative pole material can be electrographite, native graphite, carbonaceous mesophase spherules, petroleum coke, carbon fiber, thermal decomposed resins carbon etc., alloy type negative material can be silicon-base alloy, kamash alloy, germanium-base alloy, acieral, antimony-containing alloy, magnesium base alloy and other alloy, transition metal oxide negative material can be molybdenum dioxide, tungsten dioxide, nickel oxide, manganese dioxide etc.,
The particle diameter of described positive electrode powder, negative material powder can be micron order, submicron order or nanoscale;
Described gel electrolyte comprise gel electrolyte solvent, polymer, lithium salts, lithium salts solvent and one or more be selected from the additive of plasticizer, surfactant, flame-retardant additive, antioxidant, conductive additive, film for additive, anti-overcharge additive; Described positive pole gel electrolyte comprise gel electrolyte solvent, polymer for the formation of described gel electrolyte skeleton structure, lithium salts, lithium salts solvent and one or more be selected from the additive of plasticizer, surfactant, flame-retardant additive, antioxidant, conductive additive, film for additive, anti-overcharge additive; Described negative pole gel electrolyte comprise gel electrolyte solvent, polymer for the formation of described gel electrolyte skeleton structure, lithium salts, lithium salts solvent and one or more be selected from the additive of plasticizer, surfactant, flame-retardant additive, antioxidant, conductive additive, film for additive, anti-overcharge additive;
Described polymer is selected from polyoxyethylene, polymethyl acrylate, polyacrylonitrile, polymethyl methacrylate, polyvinyl chloride, polyvinyl acetate, Kynoar or Kynoar for one or more; The material of hexafluoropropylene copolymer, described gel electrolyte solvent is acetone, oxolane, dimethyl formamide or pyridine, described lithium salts is lithium hexafluoro phosphate, hexafluoroarsenate lithium, LiBF4, oxalic acid difluoro boric acid, lithium perchlorate, trifluoromethyl sulfonic acid lithium or two trifluoromethanesulfonimide lithium, and described lithium salts solvent is that one or more are selected from the solvent of propene carbonate, ethylene carbonate, diethyl carbonate, methyl ethyl carbonate, dibutyl phthalate, succinonitrile, dimethyl carbonate.
Have a preparation method for the gel electrolyte lithium ion battery of combination electrode as above, it comprises the following steps:
A, preparation gel electrolyte, composite positive pole and composite negative pole material:
Under the condition of exclusion of water and oxygen, use gel electrolyte solvent according to different ratio, polymer, lithium salts, lithium salts solvent and surfactant for the formation of described gel electrolyte skeleton structure prepare gel electrolyte, positive pole gel electrolyte, negative pole gel electrolyte respectively, described polymer can be polyoxyethylene, polymethyl acrylate, polyacrylonitrile, polymethyl methacrylate, polyvinyl chloride, polyvinyl acetate, Kynoar or Kynoar; Hexafluoropropylene copolymer, described gel electrolyte solvent can be acetone, oxolane, dimethyl formamide or pyridine, described lithium salts can be lithium hexafluoro phosphate, hexafluoroarsenate lithium, LiBF4, oxalic acid difluoro boric acid, lithium perchlorate, trifluoromethyl sulfonic acid lithium or two trifluoromethanesulfonimide lithium, and described lithium salts solvent can be selected from the solvent of propene carbonate, ethylene carbonate, diethyl carbonate, methyl ethyl carbonate, dibutyl phthalate, succinonitrile, dimethyl carbonate for one or more;
In positive pole gel electrolyte, add particle diameter is micron order, submicron order or nano level positive electrode powder, and adopt ultrasonic process or mechanical agitation mode to mix, obtain composite positive pole, in negative pole gel electrolyte, add particle diameter is again micron order, submicron order or nano level negative material powder, and adopt ultrasonic process or mechanical agitation mode to mix, obtain composite negative pole material;
Described positive electrode powder can select the powder of the traditional lithium-ion battery positive electrodes such as cobalt acid lithium, lithium iron phosphate, spinel structure LiMn2O4, nickel-cobalt-manganternary ternary anode material or nickel cobalt aluminium tertiary cathode material, and described negative material powder can select the powder of the traditional lithium-ion battery negative materials such as carbon negative pole material, silicon based anode material, alloy type negative material or transition metal oxide negative material;
B, coating composite positive pole and gel electrolyte:
Get plus plate current-collecting body 204, the aluminium foil of preferred thickness within the scope of 10-100 μm, by the coated on one side a layer thickness composite positive pole 100-10000 μm within the scope of of slot coated technique at plus plate current-collecting body 204, be coated with the gel electrolyte of a layer thickness within the scope of 0.5-100 μm thereon by slot coated technique again, namely obtain positive pole unit 207;
C, coating composite negative pole material and gel electrolyte:
Get negative current collector 201, the Copper Foil of preferred thickness within the scope of 8-100 μm, by the coated on one side a layer thickness composite negative pole material 100-10000 μm within the scope of of slot coated technique at negative current collector 201, be coated with the gel electrolyte of a layer thickness within the scope of 0.5-100 μm thereon by slot coated technique again, namely obtain negative pole unit 208;
D, assembling and encapsulation:
The gel electrolyte of infiltrate to described positive pole unit 207 and described negative pole unit 208 surface is first used to infiltrate, described positive pole unit 207 is coated with the one side that the one side of gel electrolyte and negative pole unit 208 be coated with gel electrolyte to fit tightly, carry out lamination assembling, obtain a both positive and negative polarity unit 200, namely battery cell 206 is obtained, finally battery cell 206 is encapsulated into positive terminal, the battery case of negative terminal, described plus plate current-collecting body 204 is electrically connected with the positive terminal on described battery case, described negative current collector 201 is electrically connected with the negative terminal on described battery case, namely the described gel electrolyte lithium ion battery with combination electrode is obtained.
In the present invention, gel electrolyte in combination electrode significantly improves the transport property of lithium ion in electrode, make the thickness of combination electrode can obtain preferably battery multiplying power property and electrode material effective rate of utilization in the scope of 100-10000 μm, it is very thick that the thickness of combination electrode can do, thus greatly reduce the usage quantity of positive and negative electrode collector, improve battery energy storage density and stored energy capacitance, such battery only needs a both positive and negative polarity unit can complete various power supply task
Embodiment 2
As shown in Figure 3, a kind of gel electrolyte lithium ion battery with combination electrode and preparation method thereof, its structure and embodiment 1 similar, difference is:
Described battery cell 206 comprises multiple both positive and negative polarity unit 200, adjacent both positive and negative polarity unit 200 polarity is contrary and by sharing a plus plate current-collecting body 204 or negative current collector 201 is superimposed together, each plus plate current-collecting body 204 and each negative current collector 201 are respectively equipped with exposed positive conductive lug and negative conductive lug, all positive conductive lugs and all negative conductive lugs are distinguished together with ultra-sonic welded, then are electrically connected with the positive terminal on described battery case, negative terminal respectively.
Its preparation method and embodiment 1 similar, difference is:
In stepb, after obtaining described negative pole unit 208, separately get negative current collector 201, the composite negative pole material described in one deck is coated with respectively on the two sides of the described negative current collector 201 separately got by slot coated technique, be coated with the gel electrolyte described in one deck respectively thereon by slot coated technique again, namely obtain the negative pole module 210 of double spread;
In step C, after obtaining described positive pole unit 207, separately get plus plate current-collecting body 204, the composite positive pole described in one deck is coated with respectively on the two sides of the described plus plate current-collecting body 204 separately got by slot coated technique, be coated with the gel electrolyte described in one deck respectively thereon by slot coated technique again, namely obtain the positive pole module 209 of double spread;
In step D, first hocket one or more described negative pole module 210 and one or more described positive pole module 209 lamination assembling, then lamination assembling is carried out with the described positive pole unit 207 matched or described negative pole unit 208 respectively in their both sides, namely the battery cell 206 comprising multiple both positive and negative polarity unit 200 is obtained, finally battery cell 206 is encapsulated into positive terminal, the battery case of negative terminal, and each plus plate current-collecting body 204 and each negative current collector 201 are respectively equipped with exposed positive conductive lug and negative conductive lug, first all positive conductive lugs and all negative conductive lugs are distinguished together with ultra-sonic welded, again respectively with the positive terminal on described battery case, negative terminal is electrically connected, namely the described gel electrolyte lithium ion battery with combination electrode is obtained, so just larger battery capacity can be obtained, meet the needs of special circumstances.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. one kind has the gel electrolyte lithium ion battery of combination electrode, it comprises with positive terminal, the battery case of negative terminal and the battery cell (206) be encapsulated in described battery case, it is characterized in that, described battery cell (206) comprises a both positive and negative polarity unit (200), described both positive and negative polarity unit (200) is layer structure, and successively by negative current collector (201), composite negative pole layer (202), gel electrolyte layer (205), anode composite layer (203) and plus plate current-collecting body (204) are formed by stacking, described anode composite layer (203) is formed by positive electrode powder and positive pole gel electrolyte Homogeneous phase mixing, described gel electrolyte layer (205) is the gel layer be made up of gel electrolyte, described composite negative pole layer (202) is formed by negative material powder and negative pole gel electrolyte Homogeneous phase mixing, described plus plate current-collecting body (204) is electrically connected with the positive terminal on described battery case, described negative current collector (201) is electrically connected with the negative terminal on described battery case.
2. the gel electrolyte lithium ion battery with combination electrode according to claim 1, is characterized in that, the thickness of described anode composite layer (203), described composite negative pole layer (202) is 100-10000 μm.
3. the gel electrolyte lithium ion battery with combination electrode according to claim 1, it is characterized in that, described plus plate current-collecting body (204) employing thickness is the aluminium foil of 10-100 μm, described negative current collector (201) employing thickness is the Copper Foil of 8-100 μm, and the thickness of described gel electrolyte layer (205) is 1-200 μm.
4. the gel electrolyte lithium ion battery with combination electrode according to claim 1, it is characterized in that, described positive electrode powder is that one is selected from cobalt acid lithium, lithium iron phosphate, spinel structure LiMn2O4, the powder of the anode material for lithium-ion batteries of nickel-cobalt-manganternary ternary anode material or nickel cobalt aluminium tertiary cathode material, described negative material powder is that one is selected from carbon negative pole material, silicon based anode material, lithium an-ode material, alloy type negative material, the powder of the lithium ion battery negative material in transition metal oxide negative material, described positive electrode powder, the particle diameter of described negative material powder is micron order, submicron order or nanoscale.
5. the gel electrolyte lithium ion battery with combination electrode according to claim 1, it is characterized in that, described gel electrolyte comprise gel electrolyte solvent, polymer, lithium salts, lithium salts solvent and one or more be selected from the additive of plasticizer, surfactant, flame-retardant additive, antioxidant, conductive additive, film for additive, anti-overcharge additive; Described positive pole gel electrolyte comprise gel electrolyte solvent, polymer for the formation of described gel electrolyte skeleton structure, lithium salts, lithium salts solvent and one or more be selected from the additive of plasticizer, surfactant, flame-retardant additive, antioxidant, conductive additive, film for additive, anti-overcharge additive; Described negative pole gel electrolyte comprise gel electrolyte solvent, polymer for the formation of described gel electrolyte skeleton structure, lithium salts, lithium salts solvent and one or more be selected from the additive of plasticizer, surfactant, flame-retardant additive, antioxidant, conductive additive, film for additive, anti-overcharge additive.
6. the gel electrolyte lithium ion battery with combination electrode according to claim 5, it is characterized in that, described polymer is selected from polyoxyethylene for one or more, polymethyl acrylate, polyacrylonitrile, polymethyl methacrylate, polyvinyl chloride, polyvinyl acetate, the material of Kynoar or Kynoar-hexafluoropropylene copolymer, described gel electrolyte solvent is acetone, oxolane, dimethyl formamide or pyridine, described lithium salts is lithium hexafluoro phosphate, hexafluoroarsenate lithium, LiBF4, oxalic acid difluoro boric acid, lithium perchlorate, trifluoromethyl sulfonic acid lithium or two trifluoromethanesulfonimide lithium, described lithium salts solvent is selected from propene carbonate for one or more, ethylene carbonate, diethyl carbonate, methyl ethyl carbonate, dibutyl phthalate, succinonitrile, the solvent of dimethyl carbonate.
7. the gel electrolyte lithium ion battery with combination electrode according to any one of claim 1 to 6, it is characterized in that, described battery cell (206) comprises multiple described both positive and negative polarity unit (200), and adjacent described both positive and negative polarity unit (200) polarity is contrary and by sharing a plus plate current-collecting body (204) or negative current collector (201) is superimposed together.
8. the preparation method with the gel electrolyte lithium ion battery of combination electrode according to any one of claim 1-6, it is characterized in that, it comprises the following steps:
A, preparation gel electrolyte, composite positive pole and composite negative pole material:
Prepare gel electrolyte, positive pole gel electrolyte, negative pole gel electrolyte respectively, positive electrode powder is added in positive pole gel electrolyte, and mix, obtain composite positive pole, negative material powder is added again in negative pole gel electrolyte, and mix, obtain composite negative pole material;
B, coating composite negative pole material and gel electrolyte:
Get negative current collector (201), by the composite negative pole material of slot coated technique described in coated on one side one deck of negative current collector (201), be coated with the gel electrolyte described in one deck thereon by slot coated technique again, namely obtain negative pole unit (208);
C, coating composite positive pole and gel electrolyte:
Get plus plate current-collecting body (204), by the composite positive pole of slot coated technique described in coated on one side one deck of plus plate current-collecting body (204), be coated with the gel electrolyte described in one deck thereon by slot coated technique again, namely obtain positive pole unit (207);
D, assembling and encapsulation:
Described positive pole unit (207) is coated with the one side that the one side of described gel electrolyte and described negative pole unit (208) be coated with described gel electrolyte to fit tightly, carry out lamination assembling, obtain a both positive and negative polarity unit (200), namely the battery cell (206) comprising a both positive and negative polarity unit (200) is obtained, finally described battery cell (206) is encapsulated into positive terminal, the battery case of negative terminal, described plus plate current-collecting body (204) is electrically connected with the positive terminal on described battery case, described negative current collector (201) is electrically connected with the negative terminal on described battery case, namely the described gel electrolyte lithium ion battery with combination electrode is obtained.
9. the preparation method with the gel electrolyte lithium ion battery of combination electrode according to claim 8, it is characterized in that, in step, gel electrolyte, composite positive pole and composite negative pole material is prepared under the condition of exclusion of water and oxygen, ultrasonic process or mechanical agitation mode is adopted to carry out married operation, in step D, first use the gel electrolyte of infiltrate to described positive pole unit (207) and described negative pole unit (208) surface to infiltrate, then carry out lamination assembling.
10. the preparation method with the gel electrolyte lithium ion battery of combination electrode according to claim 8, it is characterized in that, in stepb, after obtaining described negative pole unit (208), separately get negative current collector (201), the composite negative pole material described in one deck is coated with respectively on the two sides of the described negative current collector (201) separately got by slot coated technique, be coated with the gel electrolyte described in one deck respectively thereon by slot coated technique again, namely obtain the negative pole module (210) of double spread;
In step C, after obtaining described positive pole unit (207), separately get plus plate current-collecting body (204), the composite positive pole described in one deck is coated with respectively on the two sides of the described plus plate current-collecting body (204) separately got by slot coated technique, be coated with the gel electrolyte described in one deck respectively thereon by slot coated technique again, namely obtain the positive pole module (209) of double spread;
In step D, first hocket one or more described negative pole module (210) and one or more described positive pole module (209) lamination assembling, then lamination assembling is carried out with the described positive pole unit (207) matched or described negative pole unit (208) respectively in their both sides, namely obtain comprising multiple both positive and negative polarity unit (200) battery cells (206).
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