CN104466229A - Flexible lithium secondary battery and preparation method thereof - Google Patents
Flexible lithium secondary battery and preparation method thereof Download PDFInfo
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- CN104466229A CN104466229A CN201310440218.4A CN201310440218A CN104466229A CN 104466229 A CN104466229 A CN 104466229A CN 201310440218 A CN201310440218 A CN 201310440218A CN 104466229 A CN104466229 A CN 104466229A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0583—Construction or manufacture of accumulators with folded construction elements except wound ones, i.e. folded positive or negative electrodes or separators, e.g. with "Z"-shaped electrodes or separators
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention provides a flexible lithium secondary battery, comprising a flexible battery shell, a battery main body and an electrolyte, wherein the battery main body is arranged in the flexible battery shell and comprises one or more sequentially stacked electrode units; each electrode unit comprises a positive plate, a flexible diaphragm and a negative plate, the positive plate, the flexible diaphragm and the negative plate are sequentially stacked, the positive plate comprises a positive current collector and a plurality of positive active material layers arranged on the positive current collector in an array type, the negative plate comprises a negative current collector and a plurality of negative active material layers arranged on the negative current collector in the array type, the positive plate and the negative plate have correspondingly arranged array interstitial vacancies, the correspondingly arranged array interstitial vacancies are applied to bending of a flexible lithium secondary battery in a plane two-dimensional direction, and the width of each array interstitial vacancy is 5-50mm. The flexible lithium secondary battery has the advantages that the integral flexibility is excellent, the energy density is high, the battery thickness, volume and mass are small, and the battery is suitable for flexible electronic products. The invention further provides a preparation method of the flexible lithium secondary battery.
Description
Technical field
The present invention relates to flexible energy storage device field, particularly relate to a kind of flexible lithium secondary battery and preparation method thereof.
Background technology
In order to meet people's demand growing to miniaturization of electronic products, flexible wearable portable electronic products becomes following development trend, such as Electronic Paper, the display screen that can reel, electronic tag and flexible sensor etc.But the current energy storage device traditional as electric supply installation generally all uses the encapsulation of rigidity, is difficult to bend, following application in flexible electronic product can not be met.Therefore, the flexible energy storage device that can coordinate with flexible electronic product is needed badly to provide required energy storing device.
Flexible energy storage device is made up of flexible electrode, electrolyte and flexible encapsulant material etc., and wherein the exploitation of flexible electrode is the key of its development; Existing commercialization lithium secondary battery mainly uses cobalt acid lithium, LiMn2O4, LiFePO4, graphite isoreactivity material, these active materials are rigid particles, therefore the electrode adopting these active material entirety coatings to be formed all is difficult to obtain good overall flexibility, and the problem that there is the stripping of rigidity active material particle in bending process, come off, thus limit the application of these active materials in flexible energy storage device.
Summary of the invention
In view of this, embodiment of the present invention first aspect provides a kind of flexible lithium secondary battery, not there is flexibility in order to solve existing traditional lithium secondary battery, in bending process, there is the problem that rigidity active material particle is peeled off, come off, and existing traditional lithium secondary battery thickness can not meet the problem of flexible electronic product.
First aspect, embodiments provide a kind of flexible lithium secondary battery, comprise flexible battery shell and the battery main body being positioned at described flexible battery shell, and the electrolyte be poured in described flexible battery shell, described battery main body comprises the electrode unit that one or more order stacks, described multiple electrode unit is connected by lug, described electrode unit comprises the positive plate that order stacks, flexible partition and negative plate, described positive plate comprises plus plate current-collecting body and multiple array and is arranged on anode active material layer on described plus plate current-collecting body, described negative plate comprises negative current collector and multiple array and is arranged on anode active material layer on described negative current collector, described positive plate and described negative plate have the corresponding array interstitial void arranged, the array interstitial void that described correspondence is arranged is used for the bending that described flexible lithium secondary battery carries out planar direction, the width of described array interstitial void is 5mm ~ 50mm.
Compared with prior art, anode active material layer and anode active material layer array are arranged on negative or positive electrode collector by the present invention, make positive plate and negative plate have the corresponding array interstitial void arranged, thus the array interstitial void making electrode can be arranged by each correspondence carry out the bending in planar direction, the array interstitial void namely arranged with correspondence bends for kink; Because array interstitial void there is no electrode active material, thus effectively can solve the rigidity active material particle stripping that the overall coated structure of existing traditional lithium secondary battery electrode active material causes when electrode bends, the problem come off; In addition, multiple electrode units of the flexible lithium secondary battery of the present invention are arranged by stack manner, the overall flexibility of flexible lithium secondary battery not only can be controlled by the stacking number controlling flexible electrode unit, and greatly reduce the thickness of flexible lithium secondary battery itself, the use of flexible electronic product can be coordinated better.
Preferably, described anode active material layer and described anode active material layer are square.
Preferably, described anode active material layer is identical with the array set-up mode of described anode active material layer.
Preferably, the width of the array of described anode active material layer and the array interstitial void of the array of described anode active material layer in horizontal and vertical both direction is equal.
Preferably, the width of the array interstitial void of the array of described anode active material layer and described anode active material layer in horizontal and vertical both direction is 20mm.
Preferably, described battery main body comprises 1 ~ 10 electrode unit.
Preferably, described flexible partition is porous insulation membrane for polymer, and thickness is 10 ~ 50 μm.
Preferably, described flexible partition is polyalkene diaphragm, polyvinyl alcohol membranes, polyvinyl chloride membrane, Teflon septum, polystyrene barrier film, polyvinyl phenol barrier film, polymethyl methacrylate barrier film, polyimide diaphragm or PETG barrier film.
Preferably, described plus plate current-collecting body and described negative current collector are metal forming collector, and thickness is 5 ~ 50 μm.
Preferably, described anode active material layer comprises can embed/the positive electrode active materials of deintercalate lithium ions, binding agent and conductive agent, and described anode active material layer comprises can embed/the negative active core-shell material of deintercalate lithium ions, binding agent and conductive agent.
Preferably, the material of described flexible battery shell is aluminum-plastic composite membrane.
The flexible lithium secondary battery that embodiment of the present invention first aspect provides, the bending in planar direction is carried out by the array interstitial void arranged corresponding on positive plate and negative plate, cell integrated pliability is good, battery energy density is high, cell thickness, volume and quality are little, are applicable to flexible electronic product.
Second aspect, embodiments provides a kind of preparation method of flexible lithium secondary battery, comprises the following steps:
Applied on plus plate current-collecting body by array architecture by anode sizing agent, through baking, obtain positive plate after compressing tablet, described positive plate comprises multiple array and is arranged on anode active material layer on described plus plate current-collecting body;
Applied on negative current collector by array architecture by cathode size, through baking, obtain negative plate after compressing tablet, described negative plate comprises multiple array and is arranged on anode active material layer on described negative current collector; Described negative plate has the array interstitial void that arrange corresponding to described positive plate; The width of described array interstitial void is 5mm ~ 50mm;
Positive plate, flexible partition, negative plate order are stacked, and the array interstitial void on described positive plate and described negative plate of aliging, namely obtain electrode unit; Choose one or more described electrode unit to be combined by stack manner, obtain battery main body, gained battery main body is placed in flexible battery shell, and adds electrolyte, sealing, vacuumizes, obtains flexible lithium secondary battery.
The preparation method of a kind of flexible lithium secondary battery that embodiment of the present invention second aspect provides, simple to operate, cost of manufacture is low, easily realizes suitability for industrialized production.
To sum up, the flexible lithium secondary battery that embodiment of the present invention first aspect provides, anode active material layer and anode active material layer array are arranged on negative or positive electrode collector, make positive plate and negative plate have the corresponding array interstitial void arranged, thus the array interstitial void making electrode can be arranged by each correspondence carry out the bending in planar direction, the array interstitial void namely arranged with correspondence bends for kink; Because array interstitial void there is no electrode active material, thus effectively can solve the rigidity active material particle stripping that the overall coated structure of existing traditional lithium secondary battery electrode active material causes when electrode bends, the problem come off; In addition, multiple electrode unit is arranged by stack manner, the overall flexibility of flexible lithium secondary battery not only can be controlled by the stacking number controlling flexible electrode unit, and greatly reduce thickness and the volume of flexible lithium secondary battery itself, can coordinate the use of flexible electronic product better, the flexible lithium secondary battery overall flexibility that embodiment of the present invention first aspect provides is good, and battery energy density is high, cell thickness, volume and quality are little, are applicable to flexible electronic product; The preparation method of a kind of flexible lithium secondary battery that embodiment of the present invention second aspect provides, simple to operate, cost of manufacture is low, easily realizes suitability for industrialized production.
The advantage of the embodiment of the present invention will partly be illustrated in the following description, and a part is apparent according to specification, or can be known by the enforcement of the embodiment of the present invention.
Accompanying drawing explanation
Fig. 1 is the overall pictorial diagram of flexible lithium secondary battery provided by the invention;
Fig. 2 is that the flexibility of flexible lithium secondary battery provided by the invention shows schematic diagram;
Fig. 3 is the structural representation of the positive pole of the flexible lithium secondary battery of the present embodiment;
Fig. 4 is the profile of the electrode unit of the flexible lithium secondary battery of the present embodiment.
Embodiment
The following stated is the preferred implementation of the embodiment of the present invention; should be understood that; for those skilled in the art; under the prerequisite not departing from embodiment of the present invention principle; can also make some improvements and modifications, these improvements and modifications are also considered as the protection range of the embodiment of the present invention.
Embodiment of the present invention first aspect provides a kind of flexible lithium secondary battery, not there is flexibility in order to solve existing traditional lithium secondary battery, in bending process, there is the problem that rigidity active material particle is peeled off, come off, and existing traditional lithium secondary battery thickness can not meet the problem of flexible electronic product.
First aspect, embodiments provide a kind of flexible lithium secondary battery, comprise flexible battery shell and the battery main body being positioned at described flexible battery shell, and the electrolyte be poured in described flexible battery shell, described battery main body comprises the electrode unit that one or more order stacks, described multiple electrode unit is connected by lug, described electrode unit comprises the positive plate that order stacks, flexible partition and negative plate, described positive plate comprises plus plate current-collecting body and multiple array and is arranged on anode active material layer on described plus plate current-collecting body, described negative plate comprises negative current collector and multiple array and is arranged on anode active material layer on described negative current collector, described positive plate and described negative plate have the corresponding array interstitial void arranged, the array interstitial void that described correspondence is arranged is used for the bending that described flexible lithium secondary battery carries out planar direction, the width of described array interstitial void is 5mm ~ 50mm.
Compared with prior art, anode active material layer and anode active material layer array are arranged on negative or positive electrode collector by the present invention, make positive plate and negative plate have the corresponding array interstitial void arranged, thus the array interstitial void making electrode can be arranged by each correspondence carry out the bending in planar direction, the array interstitial void namely arranged with correspondence bends for kink; Because array interstitial void there is no electrode active material, thus effectively can solve the rigidity active material particle stripping that the overall coated structure of existing traditional lithium secondary battery electrode active material causes when electrode bends, the problem come off; In addition, multiple electrode units of the flexible lithium secondary battery of the present invention are arranged by stack manner, the overall flexibility of flexible lithium secondary battery not only can be controlled by the stacking number controlling flexible electrode unit, and greatly reduce the thickness of flexible lithium secondary battery itself, the use of flexible electronic product can be coordinated better.
In present embodiment, described anode active material layer and described anode active material layer are square.In other embodiments, anode active material layer and anode active material layer also can rounded, triangles etc.
In present embodiment, described anode active material layer is identical with the array set-up mode of described anode active material layer.Namely the shape of anode active material layer and anode active material layer, the parameter such as number and array interstitial void width are all identical.In other embodiments, anode active material layer also can be different from the array set-up mode of anode active material layer, and namely anode active material layer and anode active material layer are arranged to different shapes, different number, different array interstitial void width etc.
In present embodiment, the width of the array of described anode active material layer and the array interstitial void of the array of described anode active material layer in horizontal and vertical both direction is equal.In other embodiments, the array of anode active material layer and the array of the anode active material layer array interstitial void in horizontal and vertical both direction also can be arranged to different width.
In present embodiment, the width of the array interstitial void of array in horizontal and vertical both direction of described anode active material layer and described anode active material layer is 20mm.
Preferably, described battery main body comprises 1 ~ 10 electrode unit.Because multiple electrode unit is combined by stack manner, therefore can be controlled the overall flexibility of flexible lithium secondary battery by the stacking number controlling flexible electrode unit, flexible lithium secondary battery can be made to possess good overall bending performance for conservative control stacked electrodes unit number and battery possesses high electrical property after bending.
Preferably, described flexible partition is porous insulation membrane for polymer, and thickness is 10 μm ~ 50 μm.
Preferably, described flexible partition is polyalkene diaphragm, polyvinyl alcohol membranes, polyvinyl chloride membrane, Teflon septum, polystyrene barrier film, polyvinyl phenol barrier film, polymethyl methacrylate barrier film, polyimide diaphragm or PETG barrier film.
In present embodiment, the thickness of described flexible partition is 25 μm.
Preferably, described plus plate current-collecting body and described negative current collector are metal forming collector, and thickness is 5 μm ~ 30 μm.
Described metal forming collector comprises Copper Foil, aluminium foil etc.In present embodiment, described plus plate current-collecting body is preferably aluminium foil, thickness preferably 12 μm.Described negative current collector is preferably Copper Foil, thickness preferably 9 μm.
Preferably, described anode active material layer comprises can embed/the positive electrode active materials of deintercalate lithium ions, binding agent and conductive agent, and described anode active material layer comprises can embed/the negative active core-shell material of deintercalate lithium ions, binding agent and conductive agent.
Describedly to embed/positive electrode active materials of deintercalate lithium ions can be transition metal oxide lithium salts, phosphoric acid lithium salts, vanadic acid lithium salts etc., describedly to embed/negative active core-shell material of deintercalate lithium ions can be graphite, metatitanic acid lithium salts, silicon and silicon based composite material, tin and Tin Composite Material, metal oxide etc.Compare the solar cell of existing flexibility, organic batteries, the flexible lithium secondary battery of the present invention adopts traditional lithium secondary battery electrode active material, still keeps high-energy-density while lithium secondary battery can be made to possess flexibility.
As long as described binding agent can by the material of active material together with conductive agent particle bond, known adhesive substance can be used, as Kynoar (PVDF), polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose (CMC), butadiene-styrene rubber (SBR) etc.As long as described conductive agent can improve the material of surface of active material electric conductivity, known conductive agent can be used, as electrically conductive graphite class, carbon black class, carbon fiber, carbon nano-tube, Graphene, metal fine powder etc.The selection of described electrolyte does not make particular determination, existing known electrolyte.
In present embodiment, the material of described flexible battery shell is aluminum-plastic composite membrane.In other embodiments, the material of flexible battery shell also can select other soft shell material.
The flexible lithium secondary battery that embodiment of the present invention first aspect provides, the bending in planar direction is carried out by the array interstitial void arranged corresponding on positive plate and negative plate, cell integrated pliability is good, battery energy density is high, cell thickness, volume and quality are little, are applicable to flexible electronic product.
Second aspect, embodiments provides a kind of preparation method of flexible lithium secondary battery, comprises the following steps:
Applied on plus plate current-collecting body by array architecture by anode sizing agent, through baking, obtain positive plate after compressing tablet, described positive plate comprises multiple array and is arranged on anode active material layer on described plus plate current-collecting body;
Applied on negative current collector by array architecture by cathode size, through baking, obtain negative plate after compressing tablet, described negative plate comprises multiple array and is arranged on anode active material layer on described negative current collector; Described negative plate has the array interstitial void that arrange corresponding to described positive plate; The width of described array interstitial void is 5mm ~ 50mm;
Positive plate, flexible partition, negative plate order are stacked, and the array interstitial void on described positive plate and described negative plate of aliging, namely obtain electrode unit; Choose one or more described electrode unit to be combined by stack manner, obtain battery main body, gained battery main body is placed in flexible battery shell, and adds electrolyte, sealing, vacuumizes, obtains flexible lithium secondary battery.
Anode sizing agent and cathode size consist of common existing composition.In the present embodiment, anode sizing agent is prepared in the following manner: be scattered in organic solvent by positive electrode active materials, binding agent and conductive agent by weight 80 ~ 99:1 ~ 10:0 ~ 10, stirs and forms anode sizing agent; Cathode size is prepared in the following manner: be scattered in organic solvent by negative active core-shell material, binding agent and conductive agent by weight 80 ~ 99:1 ~ 10:0 ~ 10, stirs and forms cathode size.
Described coating operation is completed by coating equipment, can use known painting method, as spraying, extrusion coated, transfer coated etc.
Preferably, described anode active material layer and described anode active material layer are square.
Preferably, described anode active material layer is identical with the array set-up mode of described anode active material layer.
Preferably, the width of the array of described anode active material layer and the array interstitial void of the array of described anode active material layer in horizontal and vertical both direction is equal.
Preferably, the width of the array interstitial void of the array of described anode active material layer and described anode active material layer in horizontal and vertical both direction is 20mm.
Preferably, choose 1 ~ 10 electrode unit to be combined by stack manner.
Preferably, described flexible partition is porous insulation membrane for polymer, and thickness is 10 ~ 50 μm.
Preferably, described flexible partition is polyalkene diaphragm, polyvinyl alcohol membranes, polyvinyl chloride membrane, Teflon septum, polystyrene barrier film, polyvinyl phenol barrier film, polymethyl methacrylate barrier film, polyimide diaphragm or PETG barrier film.
More preferably, the thickness of described flexible partition is 25 μm.
Preferably, described plus plate current-collecting body and described negative current collector are metal forming collector, and thickness is 5 ~ 30 μm.
Described metal forming collector comprises Copper Foil, aluminium foil etc.Described plus plate current-collecting body is preferably aluminium foil, thickness preferably 12 μm.Described negative current collector is preferably Copper Foil, thickness preferably 9 μm.
Preferably, described anode active material layer comprises can embed/the positive electrode active materials of deintercalate lithium ions, binding agent and conductive agent, and described anode active material layer comprises can embed/the negative active core-shell material of deintercalate lithium ions, binding agent and conductive agent.
Describedly to embed/positive electrode active materials of deintercalate lithium ions can be transition metal oxide lithium salts, phosphoric acid lithium salts, vanadic acid lithium salts etc., describedly to embed/negative active core-shell material of deintercalate lithium ions can be graphite, metatitanic acid lithium salts, silicon and silicon based composite material, tin and Tin Composite Material, metal oxide etc.Compare the solar cell of existing flexibility, organic batteries, the flexible lithium secondary battery of the present invention adopts traditional lithium secondary battery electrode active material, still keeps high-energy-density while lithium secondary battery can be made to possess flexibility.
As long as described binding agent can by the material of active material together with conductive agent particle bond, known adhesive substance can be used, as Kynoar (PVDF), polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose (CMC), butadiene-styrene rubber (SBR) etc.As long as described conductive agent can improve the material of surface of active material electric conductivity, known conductive agent can be used, as electrically conductive graphite class, carbon black class, carbon fiber, carbon nano-tube, Graphene, metal fine powder etc.The selection of described electrolyte does not make particular determination, existing known electrolyte.
Preferably, the material of described flexible battery shell is aluminum-plastic composite membrane.
The preparation method of a kind of flexible lithium secondary battery that embodiment of the present invention second aspect provides, simple to operate, cost of manufacture is low, easily realizes suitability for industrialized production.
Multiple embodiment is divided to be further detailed the embodiment of the present invention below.The embodiment of the present invention is not limited to following specific embodiment.In the scope of constant principal right, carrying out that can be suitable is changed and implements.
The preferred Capacity design of the following embodiment of the present invention be 1000mAh lithium secondary battery as flexible battery prototype, selected lithium secondary battery is the known Soft Roll polymer battery of industry, as shown in Figure 1.The flexibility of the flexible lithium secondary battery that Fig. 2 provides for the embodiment of the present invention shows schematic diagram.
Embodiment one
A preparation method for flexible lithium secondary battery, comprises the following steps:
(1) cobalt acid lithium, binding agent PVDF and conductive black are mixed by weight 96:2:2, add a certain amount of organic solvent nitrogen methyl pyrrolidone, adopt planet high speed dispersor to carry out dispersion and obtain anode sizing agent, gained anode sizing agent is sprayed in aluminum foil current collector by array architecture, form multiple array and be arranged on anode active material layer in aluminum foil current collector, then obtain positive plate after baking, compressing tablet;
(2) Delanium, binding agent PVDF, conductive black are mixed by weight 95:3:2, add a certain amount of organic solvent nitrogen methyl pyrrolidone, adopt planet high speed dispersor to carry out dispersion and obtain cathode size, gained cathode size is sprayed in copper foil current collector by array architecture, form multiple array and be arranged on anode active material layer in copper foil current collector, then obtain negative plate after baking, compressing tablet;
Anode active material layer is identical with the array set-up mode of anode active material layer, and anode active material layer and anode active material layer are square; The width of the array interstitial void of anode active material layer and anode active material layer is 20mm;
(3) be that PP/PE/PP polyalkene diaphragm, the negative plate order of 25 μm stacks by above-mentioned gained positive plate, thickness, and the array interstitial void of align anode active material layer and anode active material layer and anode active material layer and anode active material layer, namely obtain electrode unit;
(4) choose 5 above-mentioned electrode units to be combined by stack manner, obtain battery main body, gained battery main body is placed in the flexible battery shell of plastic-aluminum combined membrane material, and adds electrolyte, sealing, vacuumizes, obtains flexible lithium secondary battery.
Fig. 3 is the structural representation of the positive pole of the flexible lithium secondary battery of the present embodiment.Wherein, 1 is aluminum foil current collector, and 2 is anode active material layer, and 3 is array interstitial void.In the present embodiment, anode active material layer 2 is square; The width of the array interstitial void 3 of array on A direction of principal axis (transverse direction) with B direction of principal axis (longitudinal direction) of anode active material layer 2 is 20mm.In the present embodiment, the structure of the negative pole of flexible lithium secondary battery is identical with the structure of above-mentioned positive pole.
Fig. 4 is the profile of the electrode unit of the flexible lithium secondary battery of the present embodiment.Wherein, 10 be positive plate, 30 be flexible partition, 20 for negative plate.In the present embodiment, flexible partition 30 is PP/PE/PP polyalkene diaphragm.
Embodiment two
A preparation method for flexible lithium secondary battery, comprises the following steps:
(1) LiFePO4, binding agent PVDF and conductive black are mixed by weight 96:2:2, add a certain amount of organic solvent nitrogen methyl pyrrolidone, adopt planet high speed dispersor to carry out dispersion and obtain anode sizing agent, gained anode sizing agent is sprayed in aluminum foil current collector by array architecture, form multiple array and be arranged on anode active material layer in aluminum foil current collector, then obtain positive plate after baking, compressing tablet;
(2) Delanium, binding agent PVDF, conductive black are mixed by weight 95:3:2, add a certain amount of organic solvent nitrogen methyl pyrrolidone, adopt planet high speed dispersor to carry out dispersion and obtain cathode size, gained cathode size is sprayed in copper foil current collector by array architecture, form multiple array and be arranged on anode active material layer in copper foil current collector, then obtain negative plate after baking, compressing tablet;
Anode active material layer is identical with the array set-up mode of anode active material layer, and anode active material layer and anode active material layer are square; The width of the array interstitial void of anode active material layer and anode active material layer is 20mm;
(3) be that PP/PE/PP polyalkene diaphragm, the negative plate of 25 μm superposes in order successively by above-mentioned gained positive plate, thickness, and the array interstitial void of align anode active material layer and anode active material layer and anode active material layer and anode active material layer, namely obtain electrode unit;
(4) choose multiple above-mentioned electrode unit to be combined by stack manner, obtain battery main body, gained battery main body is placed in the flexible battery shell of plastic-aluminum combined membrane material, and adds electrolyte, sealing, vacuumizes, obtains flexible lithium secondary battery.
Embodiment three
A preparation method for flexible lithium secondary battery, comprises the following steps:
(1) cobalt acid lithium, binding agent PVDF and conductive black are mixed by weight 96:2:2, add a certain amount of organic solvent nitrogen methyl pyrrolidone, adopt planet high speed dispersor to carry out dispersion and obtain anode sizing agent, gained anode sizing agent is sprayed in aluminum foil current collector by array architecture, form multiple array and be arranged on anode active material layer in aluminum foil current collector, then obtain positive plate after baking, compressing tablet;
(2) Delanium, binding agent PVDF, conductive black are mixed by weight 95:3:2, add a certain amount of organic solvent nitrogen methyl pyrrolidone, adopt planet high speed dispersor to carry out dispersion and obtain cathode size, gained cathode size is sprayed in copper foil current collector by array architecture, form multiple array and be arranged on anode active material layer in copper foil current collector, then obtain negative plate after baking, compressing tablet;
Anode active material layer is identical with the array set-up mode of anode active material layer, and anode active material layer and anode active material layer are square; The width of the array interstitial void of anode active material layer and anode active material layer is 20mm;
(3) be that PP/PE/PP polyalkene diaphragm, the negative plate of 50 μm superposes in order successively by above-mentioned gained positive plate, thickness, and the array interstitial void of align anode active material layer and anode active material layer and anode active material layer and anode active material layer, namely obtain electrode unit;
(4) choose multiple above-mentioned electrode unit to be combined by stack manner, obtain battery main body, gained battery main body is placed in the flexible battery shell of plastic-aluminum combined membrane material, and adds electrolyte, sealing, vacuumizes, obtains flexible lithium secondary battery.
Embodiment four
The difference of the present embodiment and embodiment three is only, adopts thickness to be that the polyvinylchloride barrier film of 25 μm is as flexible partition.
Embodiment five
The difference of the present embodiment and embodiment three is only, adopts thickness to be that the polyvinylchloride barrier film of 50 μm is as flexible partition.
Effect example is the beneficial effect providing powerful support for the embodiment of the present invention, provides effect example as follows, in order to evaluate and test the performance of the product that the embodiment of the present invention provides.
1, embodiment one and the flexible lithium secondary battery of embodiment two gained are carried out the electric performance test before and after flexible bending.First the front discharge capacity C1 of flexible lithium secondary battery bending is recorded, then (bending radian is 10 ~ 20 ° to carry out flexibility bending to this flexible lithium secondary battery, bending number of times is respectively 20 times, 50 times, 100 times), discharge capacity C2 after the bending of record battery, and calculated capacity conservation rate R1(R1=C2/C1); Battery after bending is continued to adopt 0.2C electric current to carry out loop test, records battery capacity C3, calculated capacity conservation rate R2=(C3/C1 after circulating for its 100 times).As shown in Table 1 and Table 2, wherein, table 1 is the electric performance test result before and after the cobalt acid lithium/Flexible graphite lithium secondary battery bending of embodiment one to result, and table 2 is the electric performance test result before and after the LiFePO4/Flexible graphite lithium secondary battery bending of embodiment two.
Table 1
The test result of table 1 shows: the embodiment of the present invention one adopts cobalt acid lithium after cell integrated bending, still to have excellent discharge capacity and battery cycle life as the flexible lithium secondary battery of the array-type electrode of positive electrode active materials.
Table 2
The test result of table 2 shows: the embodiment of the present invention two adopts LiFePO4 to contrast as the flexible battery lithium secondary of cobalt acid lithium in the flexible lithium secondary battery of the array-type electrode of positive electrode active materials and embodiment one as positive electrode active materials, after bending, discharge capacity of the cell slightly reduces, but due to the cycle performance that LiFePO 4 material self is superior, the cycle performance after battery bending is better than the result in embodiment one.
2, flexible for embodiment three ~ embodiment five gained lithium secondary battery is carried out the electric performance test before and after flexible bending.First record the front discharge capacity C1 of flexible lithium secondary battery bending, then flexibility bending 100 times (bending radian is 10 ~ 20 °) is carried out to this flexible lithium secondary battery, the rear discharge capacity C2 of record battery bending, and calculated capacity conservation rate R1(R1=C2/C1); Battery after bending is continued to adopt 0.2C electric current to carry out loop test, records battery capacity C3, calculated capacity conservation rate R2=(C3/C1 after circulating for its 100 times).Result is as shown in table 3, and table 3 is adopt thickness 25 μm of PP/PE/PP polyalkene diaphragms, thickness 50 μm of PP/PE/PP polyalkene diaphragms, thickness 25 μm of polyvinylchloride barrier films, thickness 50 μm of polyvinylchloride barrier films as the electric performance test result before and after the flexible lithium secondary battery bending of the embodiment one of flexible partition, embodiment three, embodiment four and embodiment five respectively.
Table 3
The result of table 3 shows: classification, the bending performance impact of thickness on flexible lithium secondary battery of flexible partition are very large, adopt polyalkene diaphragm PP/PE/PP battery performance to be better than polyvinylchloride, adopt thickness 50 μm of flexible partition battery performances to be better than thickness 25 μm; But consider cell integrated thickness can be caused to increase with the thickness increase of flexible partition and volume energy density is reduced, therefore flexible partition thickness preferably 25 μm simultaneously.
Claims (10)
1. a flexible lithium secondary battery, comprise flexible battery shell and the battery main body being positioned at described flexible battery shell, and the electrolyte be poured in described flexible battery shell, it is characterized in that, described battery main body comprises the electrode unit that one or more order stacks, described electrode unit comprises the positive plate that order stacks, flexible partition and negative plate, described positive plate comprises plus plate current-collecting body and array and is arranged on multiple anode active material layer on described plus plate current-collecting body, described negative plate comprises negative current collector and array and is arranged on multiple anode active material layer on described negative current collector, described positive plate and described negative plate have the corresponding array interstitial void arranged, the array interstitial void that described correspondence is arranged is used for the bending that described flexible lithium secondary battery carries out planar direction, the width of described array interstitial void is 5mm ~ 50mm.
2. flexible lithium secondary battery as claimed in claim 1, is characterized in that, described anode active material layer and described anode active material layer are square.
3. flexible lithium secondary battery as claimed in claim 1, is characterized in that, described anode active material layer is identical with the array set-up mode of described anode active material layer.
4. flexible lithium secondary battery as claimed in claim 1, is characterized in that, the width of the array of described anode active material layer and the array interstitial void of the array of described anode active material layer in horizontal and vertical both direction is equal.
5. flexible lithium secondary battery as claimed in claim 1, is characterized in that, described battery main body comprises 1 ~ 10 electrode unit.
6. flexible lithium secondary battery as claimed in claim 1, is characterized in that, described flexible partition is porous insulation membrane for polymer, and thickness is 10 μm ~ 50 μm.
7. flexible lithium secondary battery as claimed in claim 1, is characterized in that, described plus plate current-collecting body and described negative current collector are metal forming collector, and thickness is 5 μm ~ 50 μm.
8. flexible lithium secondary battery as claimed in claim 1, it is characterized in that, described anode active material layer comprises can embed/the positive electrode active materials of deintercalate lithium ions, binding agent and conductive agent, and described anode active material layer comprises can embed/the negative active core-shell material of deintercalate lithium ions, binding agent and conductive agent.
9. flexible lithium secondary battery as claimed in claim 1, is characterized in that, the material of described flexible battery shell is aluminum-plastic composite membrane.
10. a preparation method for flexible lithium secondary battery, is characterized in that, comprises the following steps:
Applied on plus plate current-collecting body by array architecture by anode sizing agent, through baking, obtain positive plate after compressing tablet, described positive plate comprises multiple array and is arranged on anode active material layer on described plus plate current-collecting body;
Applied on negative current collector by array architecture by cathode size, through baking, obtain negative plate after compressing tablet, described negative plate comprises multiple array and is arranged on anode active material layer on described negative current collector; Described negative plate has the array interstitial void that arrange corresponding to described positive plate; The width of described array interstitial void is 5mm ~ 50mm;
Positive plate, flexible partition, negative plate order are stacked, and the array interstitial void on described positive plate and described negative plate of aliging, namely obtain electrode unit; Choose one or more described electrode unit to be combined by stack manner, obtain battery main body, gained battery main body is placed in flexible battery shell, and adds electrolyte, sealing, vacuumizes, obtains flexible lithium secondary battery.
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