CN107516725A - Battery core and energy storage device - Google Patents
Battery core and energy storage device Download PDFInfo
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- CN107516725A CN107516725A CN201610430955.XA CN201610430955A CN107516725A CN 107516725 A CN107516725 A CN 107516725A CN 201610430955 A CN201610430955 A CN 201610430955A CN 107516725 A CN107516725 A CN 107516725A
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
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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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Materials Engineering (AREA)
- Cell Separators (AREA)
- Secondary Cells (AREA)
Abstract
The present invention provides a kind of battery core and energy storage device.The battery core includes positive plate, negative plate.The battery core also includes：Polymer/ceramic composite fibre porous layer, it is formed in situ by polymer and ceramic particle by electrostatic spinning on the surface of the positive plate and/or the surface of the negative plate, positive plate and negative plate is separated.Wherein, a diameter of 20nm~500nm for the nanofibers that polymer/ceramic composite fibre porous layer electrostatic spinning is formed, the particle diameter of ceramic particle are 10nm~1000nm, 0.5 times~5 times of the particle diameter of a diameter of ceramic particle of nanofibers.High rate performance, cryogenic property and the security performance having been had simultaneously using the energy storage device of the battery core of the present invention.
Description
Technical field
The present invention relates to technical field of energy storage, more particularly to a kind of battery core and energy storage device.
Background technology
The barrier film for being presently used for battery core is usually PE, PP or its composite, can after (dry or wet) by stretching
With obtain thickness it is smaller, have microcellular structure film, that is, isolate film base material.During in battery core, generally also need in base material
On one side or both sides coat certain thickness functional material (ceramics, binding agent etc.), all have to positive plate, negative plate in battery core
Preferably bond, realize better performance.
After typically to isolation film base material (such as PE, PP or its composite) stretching (dry or wet), it is possible to produce
Microcellular structure, the aperture of micropore is often tens nanometers.But intensity is influenceed after the material itself and stretching by base material, base material
Porosity is not generally high, and between 30%~50%, the structure of the micropore of base material, the distribution of micropore are uncontrollable state, and
Wherein some hole can not run through base material, can not effectively transmit electrolyte and ion.
In addition, the preparation of traditional battery core is usually to fit to pole piece after first the barrier material of commercialization is cut out,
The complex process, very high to the technical requirements of assembling, barrier material wastes that big, cost is high.Conventional barrier film using PP, PE as
Raw material, but the light and soft thin cunning of PP, PE, in the preparation process of battery core, barrier film easily slides between pole piece, often results in just
Short circuit and interracial contact between negative pole is bad.Simultaneously in the preparation process of battery core to the mechanical property requirements of barrier film compared with
Height, therefore ceramic coated is often carried out to barrier film, but the barrier film after coating has to the bond effect of positive plate, negative plate
Limit, especially poor to the bonding of negative plate, the final electrical property for influenceing battery core.
The content of the invention
In view of problem present in background technology, it is an object of the invention to provide a kind of battery core and energy storage device, uses
High rate performance, cryogenic property and the security performance that the energy storage device of the battery core has had simultaneously.
In order to achieve the above object, in one aspect of the invention, the invention provides a kind of battery core, it include positive plate,
Negative plate.The battery core also includes：Polymer/ceramic composite fibre porous layer, passes through electrostatic by polymer and ceramic particle
Spinning is formed in situ on the surface of the positive plate and/or the surface of the negative plate, and positive plate and negative plate are separated.
Wherein, a diameter of 20nm~500nm for the nanofibers that polymer/ceramic composite fibre porous layer electrostatic spinning is formed, pottery
The particle diameter of porcelain particle is 10nm~1000nm, 0.5 times~5 times of the particle diameter of a diameter of ceramic particle of nanofibers.
In another aspect of this invention, the invention provides a kind of energy storage device, it includes institute according to an aspect of the present invention
The battery core stated.
Relative to prior art, beneficial effects of the present invention are：
In the battery core of the present invention, using by polymer and ceramic particle by electrostatic spinning be formed in situ in it is described just
Polymer/ceramic composite fibre porous layer on the surface of pole piece and/or the surface of the negative plate, for separate positive plate with
Negative plate, therefore the barrier film that traditional battery core uses can be directly replaced, and the hole of the polymer/ceramic composite fibre porous layer
Gap rate is very high, has good wellability and compatibility with electrolyte, can effectively transmit ion, can improve and use the battery core
Energy storage device high rate performance and cryogenic property, in addition the polymer/ceramic composite fibre porous layer can realize and positive pole
Good interfacial adhesion between piece, negative plate, improves the hardness of the energy storage device using the battery core, and increase uses the battery core
Energy storage device security performance.
Embodiment
The following detailed description of the battery core and energy storage device according to the present invention.
Illustrate battery core according to a first aspect of the present invention first.
Battery core according to a first aspect of the present invention includes positive plate, negative plate.The battery core also includes：Polymer/ceramic
Composite fibre porous layer, by polymer and ceramic particle by electrostatic spinning be formed in situ in the surface of the positive plate and/
Or on the surface of the negative plate, positive plate and negative plate are separated.Wherein, polymer/ceramic composite fibre porous layer is quiet
A diameter of 20nm~the 500nm for the nanofibers that Electrospun is formed, the particle diameter of ceramic particle are 10nm~1000nm, Nanowire
Tie up the particle diameter of a diameter of ceramic particle of silk 0.5 times~5 times.Here the particle diameter of ceramic particle refers to the average grain of ceramic particle
Footpath D50.
In the present invention, it is formed in situ using by polymer and ceramic particle by electrostatic spinning in the positive plate
Polymer/ceramic composite fibre porous layer on surface and/or the surface of the negative plate, for separating positive plate and negative pole
Piece, therefore the barrier film (such as PE, PP barrier film) in traditional battery core can be replaced.But it can also contain in the battery core of the present invention
There is barrier film, such as barrier film can be located at pole piece (positive plate or the negative pole for being not provided with polymer/ceramic composite nano fiber layer
Piece, according to the different and different of the position of polymer/ceramic composite nano fiber layer setting) and polymer/ceramic composite Nano
Between fibrous layer.
In the present invention, because the polymer/ceramic composite fibre porous layer that electrostatic spinning technique is formed is by Nanowire
Dimension silk deposition forms, therefore porosity is very high, reaches as high as 95%, and the micropore formed is effective apearture, therefore can be with
Conductive electrolyte and ion well, improve using the battery core energy storage device dynamic performance, especially high rate performance and
Cryogenic property.
In the present invention, because the polymer/ceramic composite fibre porous layer that electrostatic spinning technique is formed is direct in-situ
The surface of positive plate and/or the surface of the negative plate are formed at, therefore can be realized between positive plate, negative plate good
Interfacial adhesion, improves the electrical property of the energy storage device using the battery core, while improves the hardness of the energy storage device using the battery core,
Increase uses the security performance of the energy storage device of the battery core.In addition, polymer/ceramic composite fibre porous layer has higher ratio
Surface area, there is good wellability and compatibility with electrolyte, be advantageous to ion transmission, can also further improve and use the electricity
The dynamic performance of the energy storage device of core.
In the present invention, the polymer/ceramic composite fibre porous layer has a higher tensile strength, and due to
A large amount of have the ceramic particle of protective effect, therefore also has good wellability, proof voltage energy and antioxygenic property.Therefore
Without making anti-oxidation processing to positive plate face re-coating ceramic layer, therefore can avoid to (such as PE, PP isolation of conventional barrier film
Film) hole have an impact, and then deteriorate using the battery core energy storage device performance.
In battery core described according to a first aspect of the present invention, the polymer/ceramic composite fibre porous layer can be formed
In on two surfaces of the positive plate.
In battery core described according to a first aspect of the present invention, the polymer/ceramic composite fibre porous layer can be formed
In on two surfaces of the negative plate.
In battery core described according to a first aspect of the present invention, the polymer/ceramic composite fibre porous layer can be formed
In on two surfaces of the positive plate and two surfaces of the negative plate.
In battery core described according to a first aspect of the present invention, the polymer/ceramic composite fibre porous layer can be formed
In on two surfaces of the positive plate and a surface of the negative plate.
In battery core described according to a first aspect of the present invention, the polymer/ceramic composite fibre porous layer can be formed
In on two surfaces of the negative plate and a surface of the positive plate.
In battery core described according to a first aspect of the present invention, can be formed on a surface of the positive plate polymer/
Ceramic composite fibrous porous layer and on the surface deviated from a surface for the positive plate of the negative plate also shape
Into polymer/ceramic composite fibre porous layer.
In battery core described according to a first aspect of the present invention, the polymer is selected from tetrafluoroethene, poly- trifluoro-ethylene, gathered
Vinylidene fluoride, polyvinyl fluoride, polyhexafluoropropylene, tetrafluoraoethylene-hexafluoropropylene copolymer, vinylidene fluoride-hexafluoropropene are common
Polymers, vinylidene fluoride-TFE copolymer, polyamide, polyimides, polyacrylonitrile, polyethylene glycol oxide, polyvinyl alcohol,
One in polyvinyl formal, polyvinyl butyral resin, polyurethane, polyphenylene oxide, epoxy resin and epoxy resin derivant
Kind is several.
In battery core described according to a first aspect of the present invention, the ceramic particle be selected from alundum (Al2O3), silica,
One or more in titanium dioxide, magnesia, zirconium oxide, barium sulfate.
In battery core described according to a first aspect of the present invention, the weight ratio of the polymer and the ceramic particle is
(2%~95%):(98%~5%).
In battery core described according to a first aspect of the present invention, the hole of the polymer/ceramic composite fibre porous layer
Rate is 20%~95%.
In battery core described according to a first aspect of the present invention, the thickness of the polymer/ceramic composite fibre porous layer
For 1 μm~30 μm.It should be noted that thickness here refers to the thickness formed in single sided deposition.
In battery core described according to a first aspect of the present invention, the positive plate include plus plate current-collecting body and positioned at it is described just
Positive electrode active material layer on the surface of pole collector, the polymer/ceramic composite fibre porous layer are formed in situ in described
On positive electrode active material layer.When the plus plate current-collecting body only one side coating positive electrode active material layer, the polymer/ceramic is answered
Condensating fiber porous layer also can be formed in situ on the plus plate current-collecting body.
In battery core described according to a first aspect of the present invention, the negative plate includes negative current collector and positioned at described negative
Negative electrode active material layer on the surface of pole collector, the polymer/ceramic composite fibre porous layer are formed in situ in described
On negative electrode active material layer.When the negative current collector only one side coating negative electrode active material layer, the polymer/ceramic is answered
Condensating fiber porous layer also can be formed in situ on the negative current collector.
In battery core described according to a first aspect of the present invention, the preparation process of polymer/ceramic composite fibre porous layer
It is as follows：By polymer and solvent, stirring and dissolving in dry environments, untill viscosity no longer rises.Ceramic particle is added afterwards,
Stir.Afterwards by electrospinning device formed nanofibers direct in-situ be deposited on the positive plate surface and/
Or on the surface of the negative plate, that is, obtain polymer/ceramic composite fibre porous layer.
In battery core described according to a first aspect of the present invention, used solvent may be selected from 1-METHYLPYRROLIDONE, N,
Dinethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO), toluene, dimethylbenzene, chlorobenzene, dichloro-benzenes, dichloromethane,
One or more in chloroform, tetrahydrofuran, acetone, methanol, ethanol, ethyl acetate, deionized water.
In battery core described according to a first aspect of the present invention, the condition of used electrostatic spinning can be：Voltage 5KV~
50KV, 20 DEG C~100 DEG C, solution flow rate 0.2mL/min~20mL/min, spinning distance 5cm~50cm of temperature, positive plate, bear
Transfer rate 10cm/min~15000cm/min of pole piece.By changing the condition of electrostatic spinning, different porosities can be obtained
Polymer/ceramic composite fibre porous layer.
Secondly the energy storage device of explanation according to a second aspect of the present invention.
Described energy storage device includes battery core described according to a first aspect of the present invention according to a second aspect of the present invention.
In energy storage device described according to a second aspect of the present invention, the energy storage device may also include pack case and electricity
Solve matter etc..
, it is necessary to which explanation, the energy storage device can be super in energy storage device described according to a second aspect of the present invention
Level capacitor, lithium rechargeable battery, sodium ion secondary battery, zinc ion secondary cell, magnesium ion secondary cell, lithium sulphur electricity
Pond, sodium-sulphur battery or magnesium sulphur battery.In an embodiment of the present invention, the implementation that energy storage device is lithium rechargeable battery is only shown
Example, but the invention is not restricted to this.
In lithium rechargeable battery, the positive plate includes plus plate current-collecting body and the positive pole on plus plate current-collecting body is lived
Property material layer.The plus plate current-collecting body is aluminium foil.The positive electrode active material layer composition is as follows, by weight, positive-active
Material:Positive conductive agent:Positive electrode binder=(92%~100%):(0%~4%):(0.5%~4%).
In lithium rechargeable battery, the positive active material is selected from cobalt acid lithium (LiCoO2), LiMn2O4, ferric phosphate
One or more in lithium, nickel cobalt manganese metal oxide (NCM).The positive conductive agent is selected from acetylene black, conductive black
One or more in (Super P, Super S, 350G etc.), carbon fiber (VGCF), CNT (CNT), Ketjen black.It is described
Positive electrode binder is selected from Kynoar (PVdF), and number-average molecular weight can be 600,000~1,200,000.
In lithium rechargeable battery, the negative plate includes negative current collector and the negative pole on negative current collector is lived
Property material layer.The negative current collector is copper foil.The negative electrode active material layer composition is as follows, by weight, negative electrode active
Material:Cathode size thickener:Cathode conductive agent:Negative electrode binder=(90%~100%):(0.2%~2%):(0%~
4%):(0.5%~4%).
In lithium rechargeable battery, the negative electrode active material is selected from Delanium or native graphite.The negative pole
Slurry thickener is selected from sodium carboxymethylcellulose, and number-average molecular weight can be for the viscosity of 100,000~400,000, the 1wt% aqueous solution
200mPaS~5000mPaS.The cathode conductive agent be selected from acetylene black, conductive black (Super P, Super S,
350G), the one or more in carbon fiber (VGCF), CNT (CNT), Ketjen black.The negative electrode binder is selected from butylbenzene
Rubber latex (Japanese Zeon, BM400B).
With reference to embodiment, the application is expanded on further.It should be understood that these embodiments be merely to illustrate the application without
For limiting scope of the present application.
Embodiment 1
(1) preparation of positive plate
Fraction meter by weight, by 96.0% positive active material LiCoO2, 2.0% positive electrode binder Kynoar,
2.0% positive conductive agent Super P are added in NMP, are stirred, and two coated in plus plate current-collecting body aluminium foil (thickness is 14 μm)
On face, positive plate is obtained after drying, roll-in, cutting, welding anode ear.
(2) preparation of negative plate
Fraction meter by weight, 95.0% negative electrode active material Delanium, the stable agent carboxymethyl of 2.0% cathode size is fine
Plain sodium, 1.0% cathode conductive agent Super P, 2.0% negative electrode binder SBR emulsion are tieed up, adds in distilled water and stirs
It is even, on the two sides coated in negative current collector copper foil (thickness is 10 μm), after drying, roll-in, cutting, welding negative electrode lug
To negative plate.
(3) preparation of electrolyte
Electrolyte includes organic solvent and lithium salts, and organic solvent is diethyl carbonate, dimethyl carbonate, ethylene carbonate
Mixture, the volume ratio of three kinds of organic solvents is 1:1:1, lithium salts LiPF6, concentration 1mol/L.
(4) preparation of polymer/ceramic composite fibre porous layer
Polymer poly vinylidene fluoride is added in 1-METHYLPYRROLIDONE, stirs, addition complete to polymer dissolving
Ceramic particle alundum (Al2O3) powder (particle diameter 40nm), stir to alundum (Al2O3) be uniformly dispersed it is stand-by.Wherein, inclined difluoro is gathered
Ethene, the weight ratio of alundum (Al2O3) are 80%:20%.Electrospinning process is used afterwards, forms nanofibers, and directly
Negative plate is placed in 150 DEG C of vacuum drying chamber heating 2h afterwards, forms polymerization by in-situ deposition on two surfaces of negative plate
Thing/ceramic composite fibrous porous layer.Wherein, deposit thickness is 20 μm/one side, and the polymer/ceramic composite fibre of formation is porous
The porosity of layer is 76%, filametntary a diameter of 120nm in the polymer/ceramic composite fibre porous layer of formation.Static Spinning
Strand part is：Voltage 20KV, 35 DEG C, solution flow rate 5mL/min, spinning distance 15cm, the transfer rate 3cm/ of negative plate of temperature
min。
(5) preparation of lithium rechargeable battery
Positive plate, the negative plate for being provided with crosslinked polymer fibers porous layer are wound into battery core, battery core is placed in packaging
In shell aluminum plastic film, baking water removal, reinject electrolyte, battery core is melted into and the process such as aging after, obtain corresponding lithium from
Sub- secondary cell.
Embodiment 2
The preparation process of lithium rechargeable battery is same as Example 1, and difference is：
(4) preparation of polymer/ceramic composite fibre porous layer
Polyvinylidene fluoride, the weight ratio of alundum (Al2O3) are 50%:50%.The polymer/ceramic composite fibre of formation
The porosity of porous layer is 73%, filametntary a diameter of 135nm in the polymer/ceramic composite fibre porous layer of formation.
Embodiment 3
The preparation process of lithium rechargeable battery is same as Example 1, and difference is：
(4) preparation of polymer/ceramic composite fibre porous layer
Polyvinylidene fluoride, the weight ratio of alundum (Al2O3) are 20%:80%.The polymer/ceramic composite fibre of formation
The porosity of porous layer is 76%, filametntary a diameter of 125nm in the polymer/ceramic composite fibre porous layer of formation.
Embodiment 4
The preparation process of lithium rechargeable battery is same as Example 1, and difference is：
(4) preparation of polymer/ceramic composite fibre porous layer
Polymer is polyvinyl fluoride.Polyvinyl fluoride, the weight ratio of alundum (Al2O3) are 20%:80%.The polymer of formation/
The porosity of ceramic composite fibrous porous layer is 82%, filametntary straight in the polymer/ceramic composite fibre porous layer of formation
Footpath is 200nm.
Embodiment 5
The preparation process of lithium rechargeable battery is same as Example 1, and difference is：
(4) preparation of polymer/ceramic composite fibre porous layer
Polymer is polyvinyl fluoride, and ceramic particle is silica (particle diameter 60nm).The weight of polyvinyl fluoride, silica
Amount is than being 20%:80%.The porosity of the polymer/ceramic composite fibre porous layer of formation is 77%, polymer/pottery of formation
Filametntary a diameter of 120nm in porcelain composite fibre porous layer.
Embodiment 6
The preparation process of lithium rechargeable battery is same as Example 1, and difference is：
(4) preparation of polymer/ceramic composite fibre porous layer
Ceramic particle is silica (particle diameter 65nm).Polyvinylidene fluoride, the weight ratio of silica are 20%:
80%.The porosity of the polymer/ceramic composite fibre porous layer of formation is 78%, the polymer/ceramic composite fibre of formation
Filametntary a diameter of 120nm in porous layer.
Comparative example 1
The preparation process of lithium rechargeable battery is same as Example 1, and difference is to substitute polymer/pottery using barrier film
Porcelain composite fibre porous layer.Barrier film is interval between positive plate and negative plate.Barrier film uses thickness as 15 μm of PP base materials,
Close to the surface coating thickness of positive plate it is 3 μm of ceramic layer in base material, close to the surface coating thickness of negative plate is 2 in base material
μm binding agent PVdF.
Comparative example 2
The preparation process of lithium rechargeable battery is same as Example 1, and difference is：
(4) preparation of polymer/ceramic composite fibre porous layer
Alundum (Al2O3) is not added, only adds polyvinylidene fluoride.The porosity of the polymer fiber porous layer of formation is
75%, filametntary a diameter of 125nm in the polymer fiber porous layer of formation.
Comparative example 3
The preparation process of lithium rechargeable battery is same as Example 1, and difference is：
(4) preparation of polymer/ceramic composite fibre porous layer
The particle diameter of alundum (Al2O3) is 240nm, and the porosity of the polymer/ceramic composite fibre porous layer of formation is
87%, filametntary a diameter of 115nm in the polymer/ceramic composite fibre porous layer of formation.
Comparative example 4
The preparation process of lithium rechargeable battery is same as Example 1, and difference is：
(4) preparation of polymer/ceramic composite fibre porous layer
Alundum (Al2O3) particle diameter is 40nm, and the porosity of the polymer/ceramic composite fibre porous layer of formation is 91%, shape
Into polymer/ceramic composite fibre porous layer in filametntary a diameter of 220nm.
Next the performance test of explanation lithium rechargeable battery.
(1) the high rate performance test of lithium rechargeable battery
Under normal temperature, with 0.5C constant-current charges to 4.35V, constant-voltage charge to 0.05C ends.0.5C constant-current discharges are to 3.0V sections
Only, discharge capacity is recorded, using this discharge capacity as 100%.
Under normal temperature, with 1.0C constant-current charges to 4.35V, constant-voltage charge to 0.05C ends, and 0.5C constant-current discharges to 3.0V are cut
Only, discharge capacity is recorded, calculates percentage.
Under normal temperature, with 2.0C constant-current charges to 4.35V, constant-voltage charge to 0.05C ends, and 0.5C constant-current discharges to 3.0V are cut
Only, discharge capacity is recorded, calculates percentage.
Under normal temperature, with 3.0C constant-current charges to 4.35V, constant-voltage charge to 0.05C ends, and 0.5C constant-current discharges to 3.0V are cut
Only, discharge capacity is recorded, calculates percentage.
(2) the low temperature performance test of lithium rechargeable battery
At 25 DEG C, with 0.5C constant-current charges to 4.35V, constant-voltage charge to 0.05C is ended, arrived with 0.5C constant-current discharges
3.0V ends, and discharge capacity is recorded, using this capacity as 100%.
At 25 DEG C, with 0.5C constant-current charges to 4.35V, constant-voltage charge to 0.05C ends, afterwards by lithium ion secondary electricity
Pond be respectively placed in -20 DEG C, -10 DEG C, in 0 DEG C of constant temperature chest, stand 2h, then put to 3.0V cut-offs, record with 0.5C constant-current discharges
Capacitance, calculate percentage.
(3) the drift bolt security performance test of lithium rechargeable battery
Under normal temperature, with 0.5C constant-current charges to 4.35V, constant-voltage charge to 0.05C ends.Using a diameter of 2.5mm nails,
With 60mm/s speed, lithium rechargeable battery is penetrated, observes the state of lithium rechargeable battery.
The high rate performance test result of the lithium rechargeable battery of table 1
| 0.5C | 1.0C | 2.0C | 3.0C | |
| Comparative example 1 | 100.0% | 91.8% | 73.9% | 49.5% |
| Comparative example 2 | 100.0% | 92.7% | 74.8% | 51.9% |
| Comparative example 3 | 100.0% | 93.1% | 75.7% | 62.3% |
| Comparative example 4 | 100.0% | 92.0% | 74.5% | 61.6% |
| Embodiment 1 | 100.0% | 91.9% | 79.6% | 69.5% |
| Embodiment 2 | 100.0% | 92.1% | 79.3% | 72.8% |
| Embodiment 3 | 100.0% | 90.9% | 76.2% | 67.3% |
| Embodiment 4 | 100.0% | 90.2% | 75.5% | 63.7% |
| Embodiment 5 | 100.0% | 89.3% | 75.4% | 60.5% |
| Embodiment 6 | 100.0% | 95.4% | 77.9% | 68.2% |
The low temperature performance test result of the lithium rechargeable battery of table 2
The drift bolt security performance test result of the lithium rechargeable battery of table 3
| It is reactionless | Mars | Burning | |
| Comparative example 1 | √ | ||
| Comparative example 2 | √ | ||
| Comparative example 3 | √ | ||
| Comparative example 4 | √ | ||
| Embodiment 1 | √ | ||
| Embodiment 2 | √ | ||
| Embodiment 3 | √ | ||
| Embodiment 4 | √ | ||
| Embodiment 5 | √ | ||
| Embodiment 6 | √ |
From table 1 to the test result of table 3 it is known that the lithium rechargeable battery use of embodiments of the invention is by polymerizeing
Thing and ceramic particle are formed in situ fine in the polymer/ceramic composite Nano on the surface of the negative plate by electrostatic spinning
Porous layer is tieed up, therefore the good rate capability of lithium rechargeable battery, low temperature performance well, security performance are high.Do not added in comparative example 2
Ceramic particle, anti-oxidant, heat-insulated effect can not be played, therefore the security performance of lithium rechargeable battery is poor.Comparative example 3
In, the ratio between the diameter of nanofibers and the particle diameter of ceramic particle are less than 0.5, and the performance of lithium rechargeable battery is poor, this
When being due to that nanofibers are thinner, because ceramic particle is relatively large, therefore actual spinning effect is poor, it is difficult to forms long-range
Nanofibers, resulting nanofibers are shorter, the intensity difference of overall nanofibrous structures, can not be sent out during drift bolt
The effect of waving.In comparative example 4, the ratio between the diameter of nanofibers and the particle diameter of ceramic particle are more than 5, the property of lithium rechargeable battery
Can be poor, when this is due to that nanofibers are thicker, most ceramic particles can be located inside nanofibers, now make pottery
Porcelain particle can not contact with electrolyte, positive plate, it is difficult to play heat-insulated, oxidation resistant function, and then can not improve lithium ion two
The security performance of primary cell.
Claims (10)
1. a kind of battery core, including positive plate, negative plate, it is characterised in that
The battery core also includes：Polymer/ceramic composite fibre porous layer, passes through electrostatic spinning by polymer and ceramic particle
It is formed in situ on the surface of the positive plate and/or the surface of the negative plate, positive plate and negative plate is separated；
Wherein, polymer/ceramic composite fibre porous layer electrostatic spinning formed nanofibers a diameter of 20nm~
500nm, the particle diameter of ceramic particle are 10nm~1000nm, 0.5 times~the 5 of the particle diameter of a diameter of ceramic particle of nanofibers
Times.
2. battery core according to claim 1, it is characterised in that the polymer is selected from tetrafluoroethene, poly- trifluoro-ethylene, gathered
Vinylidene fluoride, polyvinyl fluoride, polyhexafluoropropylene, tetrafluoraoethylene-hexafluoropropylene copolymer, vinylidene fluoride-hexafluoropropene are common
Polymers, vinylidene fluoride-TFE copolymer, polyamide, polyimides, polyacrylonitrile, polyethylene glycol oxide, polyvinyl alcohol,
One in polyvinyl formal, polyvinyl butyral resin, polyurethane, polyphenylene oxide, epoxy resin and epoxy resin derivant
Kind is several.
3. battery core according to claim 1, it is characterised in that the ceramic particle be selected from alundum (Al2O3), silica,
One or more in titanium dioxide, magnesia, zirconium oxide, barium sulfate.
4. battery core according to claim 1, it is characterised in that the weight of the polymer and ceramic particle ratio is
(2%~95%):(98%~5%).
5. battery core according to claim 1, it is characterised in that the hole of the polymer/ceramic composite fibre porous layer
Rate is 20%~95%.
6. battery core according to claim 1, it is characterised in that the thickness of the polymer/ceramic composite fibre porous layer
For 1 μm~30 μm.
7. battery core according to claim 1, it is characterised in that the positive plate include plus plate current-collecting body and positioned at it is described just
Positive electrode active material layer on the surface of pole collector, the polymer/ceramic composite fibre porous layer are formed in situ in described
On positive electrode active material layer.
8. battery core according to claim 1, it is characterised in that the negative plate includes negative current collector and positioned at described negative
Negative electrode active material layer on the surface of pole collector, the polymer/ceramic composite fibre porous layer are formed in situ in described
On negative electrode active material layer.
9. a kind of energy storage device, it is characterised in that including the battery core according to any one of claim 1-8.
10. energy storage device according to claim 9, it is characterised in that the energy storage device is ultracapacitor, lithium ion
Secondary cell, sodium ion secondary battery, zinc ion secondary cell, magnesium ion secondary cell, lithium-sulfur cell, sodium-sulphur battery or magnesium sulphur
Battery.
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| CN201610430955.XA CN107516725A (en) | 2016-06-16 | 2016-06-16 | Battery core and energy storage device |
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| CN201610430955.XA CN107516725A (en) | 2016-06-16 | 2016-06-16 | Battery core and energy storage device |
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| CN110120483A (en) * | 2019-05-10 | 2019-08-13 | 中原工学院 | A kind of sodium-ion battery diaphragm and preparation method thereof |
| CN110635093A (en) * | 2019-08-30 | 2019-12-31 | 电子科技大学 | Lithium-sulfur battery anode and diaphragm integrated structure and preparation method thereof |
| CN111864275A (en) * | 2019-04-26 | 2020-10-30 | 北京卫蓝新能源科技有限公司 | Battery cell, preparation method thereof and lithium ion battery |
| CN112397716A (en) * | 2020-07-31 | 2021-02-23 | 湖北亿纬动力有限公司 | Oily ceramic slurry, preparation method thereof, positive plate coated with slurry and lithium ion battery |
| CN113140868A (en) * | 2021-04-22 | 2021-07-20 | 中南大学 | In-situ inorganic-organic composite spinning diaphragm and preparation method and application thereof |
| WO2021189469A1 (en) * | 2020-03-27 | 2021-09-30 | 宁德新能源科技有限公司 | Electrochemical device |
| CN114583181A (en) * | 2022-03-18 | 2022-06-03 | 江苏天合储能有限公司 | Composite current collector for lithium battery and preparation method thereof |
| CN115088127A (en) * | 2020-03-27 | 2022-09-20 | 宁德新能源科技有限公司 | Electrochemical device |
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| CN111864275A (en) * | 2019-04-26 | 2020-10-30 | 北京卫蓝新能源科技有限公司 | Battery cell, preparation method thereof and lithium ion battery |
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| CN110120483A (en) * | 2019-05-10 | 2019-08-13 | 中原工学院 | A kind of sodium-ion battery diaphragm and preparation method thereof |
| CN110635093A (en) * | 2019-08-30 | 2019-12-31 | 电子科技大学 | Lithium-sulfur battery anode and diaphragm integrated structure and preparation method thereof |
| WO2021189469A1 (en) * | 2020-03-27 | 2021-09-30 | 宁德新能源科技有限公司 | Electrochemical device |
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| CN115088127B (en) * | 2020-03-27 | 2024-03-19 | 宁德新能源科技有限公司 | Electrochemical device |
| CN112397716A (en) * | 2020-07-31 | 2021-02-23 | 湖北亿纬动力有限公司 | Oily ceramic slurry, preparation method thereof, positive plate coated with slurry and lithium ion battery |
| CN113140868A (en) * | 2021-04-22 | 2021-07-20 | 中南大学 | In-situ inorganic-organic composite spinning diaphragm and preparation method and application thereof |
| CN114583181A (en) * | 2022-03-18 | 2022-06-03 | 江苏天合储能有限公司 | Composite current collector for lithium battery and preparation method thereof |
| CN114583181B (en) * | 2022-03-18 | 2024-02-27 | 江苏天合储能有限公司 | Composite current collector for lithium battery and preparation method thereof |
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Application publication date: 20171226 |