CN108321360A - Positive electrode slurry, positive plate and energy storage device - Google Patents
Positive electrode slurry, positive plate and energy storage device Download PDFInfo
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- CN108321360A CN108321360A CN201710035982.1A CN201710035982A CN108321360A CN 108321360 A CN108321360 A CN 108321360A CN 201710035982 A CN201710035982 A CN 201710035982A CN 108321360 A CN108321360 A CN 108321360A
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- plasticizer
- positive
- sizing agent
- diaphragm
- anode sizing
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention provides a positive electrode slurry, a positive electrode plate and an energy storage device. The positive electrode slurry includes a positive electrode active material, a conductive agent, a binder, and N-methylpyrrolidone. The positive electrode slurry further includes a plasticizer. The plasticizer is miscible with N-methyl pyrrolidone. The plasticizer is liquid at room temperature. The boiling point of the plasticizer is not lower than 150 ℃ and the flash point of the plasticizer is not lower than 110 ℃. The molecular structure of the plasticizer contains polar functional groups, and the polar functional groups comprise one or more of-OH, -COOH and- (C ═ O) O-. The crystallinity of the glue film formed by the plasticizer and the polyvinylidene fluoride is smaller than that of the glue film formed by the polyvinylidene fluoride. The plasticizer disclosed by the invention can improve the flexibility of the positive membrane and reduce the risks of winding and hot pressing of the positive membrane and light leakage in a folding manner. The plasticizer does not deteriorate the adhesive force between the positive diaphragm and the positive current collector and the resistance of the positive diaphragm.
Description
Technical field
The present invention relates to a kind of energy storage device field more particularly to anode sizing agent, positive plate and energy storage devices.
Background technology
As universal and national policy the guiding of electric vehicle/electric bus and the huge market demand have pushed lithium
The technical research of ion secondary battery and application.Electric vehicle (EV) is to be concerned with the cruising ability of lithium rechargeable battery
Focus, focus on research direction one of of the high-energy density as lithium rechargeable battery is that improve lithium rechargeable battery continuous
The important measure of boat ability.
Currently, the compacted density for improving positive/negative plate is to improve the effective side of lithium rechargeable battery energy density
Method, but the energy density of lithium rechargeable battery is improved, the cold pressing pressure for improving positive/negative plate is theoretically needed, not only to cold
It presses machine utilization big, and cold pressing process can be such that the extension of positive and negative anodes diaphragm increases, substantially increases to process in cold pressing process and break
The risk of band.The energy density of lithium rechargeable battery is improved simultaneously, can further be deteriorated positive/negative plate brittleness, be made positive/negative plate
It is susceptible to inner ring fracture in the process of winding hot pressing, all can to the chemical property and security performance of lithium rechargeable battery
It impacts.
Invention content
The problem of in view of background technology, of the invention one be designed to provide a kind of anode sizing agent, positive plate and
Energy storage device, the plasticizer make the anode sizing agent have good coating waste water performance, while can reduce positive diaphragm
Required pressure when cold pressing reduces the extension of positive diaphragm, reduces the risk that broken belt is processed in cold pressing process.
Another object of the present invention is to provide a kind of anode sizing agent, positive plate and energy storage device, the plasticizer can change
The flexibility of kind anode diaphragm reduces the risk of positive diaphragm winding hot pressing and doubling light leakage.
Another object of the present invention is to provide a kind of anode sizing agent, positive plate and energy storage device, the plasticizer plus
Entering will not make the cohesive force between positive diaphragm and plus plate current-collecting body be deteriorated, and the resistance of positive diaphragm will not be made to be deteriorated.
In order to achieve the above object, in one aspect of the invention, the present invention provides a kind of anode sizing agents comprising anode
Active material, conductive agent, binder and N-Methyl pyrrolidone.The anode sizing agent further includes plasticizer.The plasticizer
It dissolves each other with N-Methyl pyrrolidone.The plasticizer is at room temperature liquid, the boiling point of the plasticizer is not less than 150 DEG C and institute
The flash-point for stating plasticizer is not less than 110 DEG C.Contain polar functional group, the polar functional group in the molecular structure of the plasticizer
Including one or more of-OH ,-COOH ,-(C=O) O-.The crystallization for the glued membrane that the plasticizer is formed with Kynoar
Degree is less than the crystallinity for the glued membrane that Kynoar itself is formed.
In another aspect of this invention, the present invention provides a kind of positive plates comprising plus plate current-collecting body and cathode film
Piece.The anode diaphragm is arranged on the surface of the plus plate current-collecting body.The anode diaphragm is by institute according to an aspect of the present invention
The anode sizing agent stated is formed.
In still another aspect of the invention, the present invention provides a kind of energy storage devices comprising according to a further aspect of the invention
The positive plate.
Compared with the existing technology, beneficial effects of the present invention are：
The plasticizer of the present invention makes the anode sizing agent have good coating waste water performance, while can reduce cathode film
Piece pressure required when being cold-pressed reduces the extension of positive diaphragm, reduces the risk that broken belt is processed in cold pressing process.
The plasticizer of the present invention can improve the flexibility of positive diaphragm, reduce positive diaphragm winding hot pressing and doubling light leakage
Risk.
The addition of the plasticizer of the present invention will not make the cohesive force between positive diaphragm and plus plate current-collecting body be deteriorated, and will not make
The resistance of positive diaphragm is deteriorated.
Description of the drawings
Fig. 1 is positive diaphragm cold pressure procedure schematic diagram；
Fig. 2 is the vertical view of positive plate.
Wherein, the reference numerals are as follows：
1 pressure roller
2 positive diaphragms
3 plus plate current-collecting bodies
Specific implementation mode
The following detailed description of anode sizing agent according to the present invention, positive plate and energy storage device.
Illustrate anode sizing agent according to a first aspect of the present invention first.
Anode sizing agent according to a first aspect of the present invention includes positive active material, conductive agent, binder and N- methyl
Pyrrolidones (NMP is used as solvent).The anode sizing agent further includes plasticizer.The plasticizer is mutual with N-Methyl pyrrolidone
It is molten.The plasticizer is at room temperature the boiling point of liquid, the plasticizer not less than 150 DEG C and the flash-point of the plasticizer is not low
In 110 DEG C.Contain polar functional group in the molecular structure of the plasticizer, the polar functional group includes-OH ,-COOH ,-(C
One or more of=O) O-.The crystallinity for the glued membrane that the plasticizer is formed with Kynoar is less than Kynoar certainly
The crystallinity for the glued membrane that body is formed.
In the anode sizing agent described according to a first aspect of the present invention, the plasticizer can be in of positive active material
Between grain and particle, between the particle and particle of conductive agent and between the particle and the particle of positive active material of conductive agent
Play the role of lubrication on contact interface and reduce frictional force, so as to reduce positive diaphragm cold pressing when institute under same compacted density
The pressure needed, reduces the degree of stretch of positive diaphragm, and then reduces the risk that broken belt is processed in cold pressing process.Meanwhile the increasing
Mould agent molecular structure in contain polar functional group, can enter binder (such as common Kynoar) strand it
Between, the tie-point of plasticizer and Kynoar is formed, the tie-point between Kynoar strand is replaced, it is poly- to reduce
Active force between vinylidene strand reduces the crystallinity and rigidity of Kynoar, to improve Kynoar
Flexibility, and then improve the flexibility of positive diaphragm, reduce winding hot pressing and inner ring occur to compromise positive plate being broken light leakage
And the risk of broken belt is processed in cold pressing process.In addition, the fusing point of the plasticizer is low, it is at room temperature liquid, and the increasing
Moulding in the molecular structure of agent can dissolve each other containing polar functional group (- OH ,-COOH ,-(C=O) O-) with NMP, therefore can ensure just
Pole slurry has good stirring and coating waste water performance.In addition, the plasticizer flash-point is high, boiling point is high, not volatile or sudden strain of a muscle
Combustion will not bring processing or safety problem during anode sizing agent coating is either dried.The plasticizer is nontoxic simultaneously
Environmental protection will not injure the personal safety of operation employee, meet the environmental requirement of passenger car indoor gas discharge.
In the anode sizing agent described according to a first aspect of the present invention, it is preferable that the plasticizer may include polyethylene glycol,
One or more of epoxidized soybean oil, tributyl citrate, tributyl 2-acetylcitrate.
In the anode sizing agent described according to a first aspect of the present invention, the binder may include Kynoar
(PVDF), the Kynoar can be selected from one or more of vinylidene fluoride homopolymer, vinylidene fluoride copolymers.It is preferred that
Ground, the vinylidene fluoride copolymers are selected from vinylidene difluoride-hexafluoropropylene copolymer, vinylidene-tetrafluoroethylene-propylene ternary
One kind in copolymer, biasfluoroethylene-hexafluoropropylene-tetrafluoroethylene terpolymer, vinylidene-chlorotrifluoroethylene
Or it is several.
In the anode sizing agent described according to a first aspect of the present invention, the quality of the plasticizer and the positive electrode active material
The ratio between matter, quality summation of conductive agent, binder and plasticizer are (0.5~5):100, plasticizer can be effective within this range
The flexibility for improving positive diaphragm more meets energy storage device to reach the risk for reducing the energy storage device electrochemistry loss of energy
Application demand.If the too high levels of plasticizer, the DC/AC impedance of positive diaphragm can be caused to increase, to influence to store up
The chemical property of energy device, while the increase of plasticizer loading can also make the bonding between positive diaphragm and plus plate current-collecting body strong
Degree reduces, and so that energy storage device is occurred the risk of processing picking during preparation and use, influences the safety of energy storage device
Energy；If plasticizer loading is too low or does not contain plasticizer, the flexible effect of the positive diaphragm of improvement is not had, is stored up to improving
The chemical property and security performance of energy device are unfavorable.
According to a first aspect of the present invention in the anode sizing agent, the type and content of the conductive agent is unrestricted, tool
Body, the conductive agent can be selected from conductive black, superconduction carbon black, electrically conductive graphite, acetylene black, Ketjen black, graphene, carbon nanotube
One or more of.
According to a first aspect of the present invention in the anode sizing agent, the type and content of the positive active material is unrestricted
System, specifically, the positive active material can be selected from lithium and cobalt oxides, lithium nickel oxide, lithium manganese oxide, Li-Ni-Mn-O
One or more of object, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, LiFePO4.
Secondly the positive plate of explanation according to a second aspect of the present invention.
Positive plate according to a second aspect of the present invention includes plus plate current-collecting body and positive diaphragm.The anode diaphragm setting
On the surface of the plus plate current-collecting body.The anode diaphragm is is formed by the anode sizing agent described in first aspect present invention.
In the positive plate described according to a second aspect of the present invention, the anode sizing agent is evenly applied to plus plate current-collecting body
On, solvent NMP is dried and removed, then obtains positive plate by processes such as cold pressings.
In the positive plate described according to a second aspect of the present invention, the anode diaphragm may be provided at the plus plate current-collecting body
One or both sides on.
In the positive plate described according to a second aspect of the present invention, referring to Figures 1 and 2, in the cold pressure procedure of positive plate,
Positive plate is acted on by the radial pressure N and tangential frictional force f of pressure roller 1, due to the thickness one of positive plate in cold pressure procedure
It directly changes, pressure N and frictional force f can be decomposed into the component N of horizontal direction respectivelyxAnd fxAnd the component of vertical direction
NyAnd fy.Wherein, component NxIt is the principal element for influencing 2 degree of stretch of positive diaphragm, the degree of stretch of plus plate current-collecting body 3 wants small
Cause positive plate cold due to the degree of stretch difference of positive diaphragm 2 and plus plate current-collecting body 3 in the degree of stretch of positive diaphragm 2
It presses and easily occurs processing broken belt in process.Plasticizer is added in anode sizing agent, can improve the particle of positive active material with
Between grain, between the particle and particle of conductive agent and the lubrication journey between the particle and the particle of positive active material of conductive agent
Degree reduces interface friction force, reduces pressure required when cold pressing, then reduces horizontal component Nx, reduce the extension of positive diaphragm 2
Degree reduces the degree of stretch difference of positive diaphragm 2 and plus plate current-collecting body 3, reduces processing broken belt in positive plate cold pressing process
Risk, while mitigating pressure roller 1 and grinding roller and hindering roller phenomenon caused by being in high pressure operating mode for a long time.Meanwhile plasticizer can be into
Between the strand for entering binder (such as common VDF homopolymers or copolymer), the connection of plasticizer and Kynoar is formed
Node replaces the tie-point between Kynoar strand, reduces the active force between Kynoar strand, reduces poly-
The crystallinity and rigidity of vinylidene to improve the flexibility of Kynoar, and then improve the flexibility of positive diaphragm 2,
This can also reduce required pressure when cold pressing, reduce winding hot pressing and inner ring fracture light leakage and cold occur to compromise positive plate
Press the risk that broken belt is processed in process.
In the positive plate described according to a second aspect of the present invention, the plus plate current-collecting body can be selected from aluminium foil, nickel foil or not
Become rusty steel foil.
Illustrate energy storage device according to a third aspect of the present invention again.
The energy storage device includes the positive plate described according to a second aspect of the present invention according to a third aspect of the present invention.
In the energy storage device described according to a third aspect of the present invention, the energy storage device further include negative plate, isolation film,
Pack case and electrolyte etc..
In the energy storage device described according to a third aspect of the present invention, it should be noted that the energy storage device can be super
Grade capacitor, lithium rechargeable battery, sodium ion secondary battery.In an embodiment of the present invention, only show that energy storage device is lithium
The embodiment of ion secondary battery, however, the present invention is not limited thereto.
In a lithium ion secondary battery, the negative plate includes negative current collector and the negative electrode film on negative current collector
Piece.The negative current collector can be copper foil.
In a lithium ion secondary battery, the negative electrode active material can be selected from artificial graphite or natural graphite.It is described negative
Pole conductive agent can be selected from acetylene black, conductive black (Super P, Super S, 350G), carbon fiber (VGCF), carbon nanotube
(CNT), one or more of Ketjen black.
In a lithium ion secondary battery, the specific type of the isolation film is not particularly limited, can be according to practical need
It asks and is selected.
In a lithium ion secondary battery, the electrolyte can be liquid electrolyte or polymer dielectric.The liquid electric
Solution matter may include lithium salts and organic solvent.
In a lithium ion secondary battery, the specific type of the lithium salts is unrestricted.Specifically, the lithium salts can be selected from
LiPF6、LiBF4、LiN(SO2F)2(being abbreviated as LiFSI), LiN (CF3SO2)2(being abbreviated as LiTFSI), LiClO4、LiAsF6、LiB
(C2O4)2(being abbreviated as LiBOB), LiBF2C2O4One or more of (being abbreviated as LiDFOB).
In a lithium ion secondary battery, the specific type of the organic solvent is not particularly limited, can be according to reality
Demand is selected.Preferably, using non-aqueous organic solvent.The non-aqueous organic solvent may include any kind carbonic ester,
Carboxylate.Carbonic ester may include cyclic carbonate or linear carbonate.The non-aqueous organic solvent may also include carbonic ester
Halogenated compound.Specifically, the organic solvent is selected from ethylene carbonate (EC), propene carbonate (PC), butylene carbonate, carbon
Sour Asia pentyl ester, fluoroethylene carbonate, dimethyl carbonate, diethyl carbonate (DEC), dipropyl carbonate, methyl ethyl carbonate, γ-
One or more of butyrolactone, methyl formate, Ethyl formate, ethyl propionate, propyl propionate, tetrahydrofuran.
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.The case where energy storage device is lithium rechargeable battery, but the present invention are only shown in embodiment
It is without being limited thereto.
In the following embodiments, reagent, material and the instrument used such as not special explanation, it is commercially available to obtain
.
Embodiment 1
As mass fraction, by 97% positive active material Li (Ni0.6Co0.2Mn0.2)O2, 1% the inclined fluorine second of binder
Polyamino alkenyl object, 1.5% conductive agent conductive black, 0.5% plasticizer polyethylene glycol (400) dry-mixed stirring, are then added molten
It is stirred evenly in agent NMP, obtains anode sizing agent, anode sizing agent is uniformly coated on plus plate current-collecting body aluminium foil later, is then existed
It is cold-pressed after being dried at 85 DEG C, obtains the positive plate that compacted density is 3.5g/cc.
Embodiment 2
The preparation of positive plate with embodiment 1, difference lies in,
As mass fraction, 96.5% positive electrode active materials Li (Ni are added0.6Co0.2Mn0.2)O2, 1% binder it is inclined
Fluoride homopolymer, 1.5% conductive agent conductive black, 1% plasticizer polyethylene glycol (400).
Embodiment 3
The preparation of positive plate with embodiment 1, difference lies in,
As mass fraction, 94.5% positive electrode active materials Li (Ni are added0.6Co0.2Mn0.2)O2, 1% binder it is inclined
Fluoride homopolymer, 1.5% conductive agent conductive black, 3% plasticizer polyethylene glycol (400).
Embodiment 4
The preparation of positive plate with embodiment 1, difference lies in,
As mass fraction, 92.5% positive electrode active materials Li (Ni are added0.6Co0.2Mn0.2)O2, 1% binder it is inclined
Fluoride homopolymer, 1.5% conductive agent conductive black, 5% plasticizer polyethylene glycol (400).
Embodiment 5
The preparation of positive plate with embodiment 1, difference lies in,
As mass fraction, 96.5% positive electrode active materials Li (Ni are added0.6Co0.2Mn0.2)O2, 1% binder it is inclined
Fluoride homopolymer, 1.5% conductive agent conductive black, 1% plasticizer epoxidized soybean oil.
Embodiment 6
The preparation of positive plate with embodiment 1, difference lies in,
As mass fraction, 96.5% positive electrode active materials Li (Ni are added0.6Co0.2Mn0.2)O2, 1% binder it is inclined
Fluoride homopolymer, 1.5% conductive agent conductive black, 1% plasticizer citric acid three ester.
Embodiment 7
The preparation of positive plate with embodiment 1, difference lies in,
As mass fraction, 96.5% positive electrode active materials Li (Ni are added0.6Co0.2Mn0.2)O2, 1% binder it is inclined
Fluoride homopolymer, 1.5% conductive agent conductive black, 1% three ester of plasticizer acetyl tributyl citrate.
Embodiment 8
The preparation of positive plate with embodiment 1, difference lies in,
Binder is selected from vinylidene difluoride-hexafluoropropylene copolymer (VDF-HFP).
Comparative example 1
The preparation of positive plate with embodiment 1, difference lies in,
As mass fraction, 97.5% positive electrode active materials Li (Ni are added0.6Co0.2Mn0.2)O2, 1% binder it is inclined
Fluoride homopolymer, 1.5% conductive agent conductive black, be added without plasticizer.
Comparative example 2
The preparation of positive plate with embodiment 1, difference lies in,
As mass fraction, 91.5% positive electrode active materials Li (Ni are added0.6Co0.2Mn0.2)O2, 1% binder it is inclined
Fluoride homopolymer, 1.5% conductive agent conductive black, 6% plasticizer polyethylene glycol (400).
Comparative example 3
The preparation of positive plate with embodiment 1, difference lies in,
As mass fraction, 96.5% positive electrode active materials Li (Ni are added0.6Co0.2Mn0.2)O2, 1% binder it is inclined
Fluoride homopolymer, 1.5% conductive agent conductive black, 1% plasticizer dimethicone.
Comparative example 4
The preparation of positive plate with embodiment 1, difference lies in,
As mass fraction, 96.5% positive electrode active materials Li (Ni are added0.6Co0.2Mn0.2)O2, 1% binder it is inclined
Fluoride homopolymer, 1.5% conductive agent conductive black, 1% plasticizer sulfolane.
The test process of positive plate will be illustrated next.
(1) the crystallinity test of PVDF glued membranes
PVDF (vinylidene fluoride homopolymer or vinylidene fluoride copolymers) according to embodiment 1-8 and comparative example 1-4 and plasticising
PVDF, plasticizer and solvent NMP are added in agitator tank (wherein, plasticizer is not added for comparative example 1) content ratio of agent, if
It is 25r/min, rate of dispersion 1500r/min, mixing time 6h to set mixing speed, completes glue and makes.Later by glue
6h is dried at 80 DEG C, and obtained PVDF glued membranes are subjected to DSC tests, obtain the crystallinity of PVDF glued membranes.Every group of test 5 times, takes
Average value.
(2) test of positive diaphragm elongation percentage
The aluminium foil of positive plate both sides of the edge is removed, is then drawn on positive plate and 3 sections of smooth straight lines is taken (anode cannot to be pierced through
Diaphragm), straight line parallel measures 3 sections of straight lengths, is denoted as L1, L2, L3 respectively in the length direction of positive diaphragm；By positive plate
It is placed on cold press and is cold-pressed, adjustment cold pressing parameter ensures that the practical compacted density of positive diaphragm is 3.5g/cc, measures cold
The length of this 3 sections of straight lines after pressure, is denoted as L1 ', L2 ', L3 ' respectively.Positive diaphragm is calculated according to E=(L '-L)/L formula to extend
As a result rate is denoted as E1, E2, E3 respectively, three data are averaged, and are denoted as the practical elongation percentage of positive diaphragm.
(3) positive diaphragm winding hot pressing test
By positive plate, isolation film, negative plate (graphite, acetylene black, SBR, CMC in mass ratio 96:1:1:1 is prepared) volume
It is coiled into the battery core of square, 60 DEG C later, carry out hot pressing under 0.4MPa pressure, battery core is disassembled later, observes and whether is leaked at folding line
Light, wherein in the battery core that winding obtains, amount to 45 folding lines.Every group of test 5 times, is averaged.
(4) positive diaphragm doubling test
Weight will be used to be pressure roller roll-in 3 times back and forth of 2Kg after positive diaphragm doubling, later paved positive diaphragm, weight
Multiple aforesaid operations, until fold position light leakage, records folds.Every group of test 5 times, is averaged.
(5) test of 180 ° of shear strengths of positive diaphragm
Positive plate is cut into the rectangle of long 100mm, width 20mm.It is the stainless steel plate of 30mm to take a width, and patch is two-sided
Glue (long 9mm, width 9mm) pastes the positive plate cut out on double faced adhesive tape on stainless steel, with 2Kg pressure rollers in positive plate
Surface rolls 3 times (300mm/min) back and forth.The sample is fixed on testing machine, pole piece axis direction is kept with force direction
Unanimously, testing machine is loaded with 10mm/min peeling rates, until positive plate is broken, stops test, record maximum shear stress is F
(unit N), bond area S=9mm × 9mm=81mm2, according to P=F/S, calculate shear strength P (units MPa).
(6) resistance test of positive diaphragm
The resistance of positive diaphragm is tested using CRM-01 pole piece resistance meters.Every group of test 5 times, is averaged.
The performance test results of table 1 embodiment 1-8 and comparative example 1-4
In the test of positive plate, the degree of stretch of positive diaphragm is characterized using the elongation percentage of positive diaphragm, wherein anode
The elongation percentage of diaphragm is bigger, then degree of stretch is bigger.With the crystallinity of PVDF glued membranes, positive diaphragm doubling light leakage number and volume
The flexibility of positive diaphragm is characterized around hot pressing folding line light leakage number.Wherein, the crystallinity of PVDF glued membranes is lower, positive diaphragm it is soft
Toughness is bigger；Positive diaphragm doubling light leakage number is more, and the flexibility of positive diaphragm is bigger；In positive diaphragm winding hot pressing, folding
Trace light leakage number is fewer, and the flexibility of positive diaphragm is bigger.With 180 ° of positive diaphragms of peel strength characterization of positive diaphragm and anode
Cohesive force between collector, peel strength is bigger, indicates that cohesive force is better between positive diaphragm and plus plate current-collecting body.With anode
The electronic conductivity of the resistance characterization anode diaphragm of diaphragm, wherein the resistance of positive diaphragm is smaller, the electronic conductance of positive diaphragm
Rate is better.
From the test result of table 1 it is found that under identical compacted density, compared with the comparative example 1 of not plasticizer-containing, implement
Required pressure is substantially reduced when the positive diaphragm cold pressing of example 1-8, and the elongation percentage of positive diaphragm is substantially reduced, and is greatly reduced cold
Press the risk that broken belt is processed in process；Positive diaphragm winding hot pressing folding line light leakage time number is substantially reduced, positive diaphragm doubling leakage
Light number obviously increases, and the crystallinity of PVDF glued membranes is greatly reduced, and the flexibility of positive diaphragm is obviously improved；Positive diaphragm with just
The resistance of cohesive force and positive diaphragm between the collector of pole is not obviously deteriorated, and can still meet normal use demand；Together
When anode sizing agent have good coating waste water performance.
In embodiment 1-4, with the increase of plasticizer polyethylene glycol (400) content, the elongation percentage of positive diaphragm reduces,
The flexibility of positive diaphragm is obviously improved, but the cohesive force between positive diaphragm and plus plate current-collecting body continuously decreases, while anode
The resistance of diaphragm gradually increases, but can still meet the use demand of positive plate, while content increases the processing to anode sizing agent
Performance does not influence, and in contrast, the comprehensive performance of the positive diaphragm containing 1% plasticizer polyethylene glycol (400) is best.And it is right
In ratio 2, plasticizer loading is excessively high, then the resistance of positive diaphragm can be caused to become larger, under the chemical property for causing energy storage device
Drop is serious, meanwhile, the shear strength of positive diaphragm reduces, i.e., the adhesion strength between positive diaphragm and plus plate current-collecting body reduces,
The risk that processing picking is occurred during the processing of positive plate and use, influences the security performance of energy storage device.
In comparative example 3, the polarity of plasticizer dimethicone is relatively low, incompatible with solvent NMP, is coated in anode sizing agent
It is susceptible to dimethicone and NMP laminations in the process, leads to anode sizing agent coating waste water poor performance, can not be coated with, this
Outside, since dimethicone is incompatible with solvent NMP, PVDF glued membranes cannot be made, therefore without the number of PVDF glued membrane crystallinity
According to.
In comparative example 4, plasticizer sulfolane is solid at room temperature, leads to anode sizing agent coating waste water poor performance, can not
Coating, and sulfolane is not substantially reduced the crystallinity of PVDF glued membranes, while positive diaphragm doubling light leakage number is still relatively low
(being only 1.8), the flexibility of positive diaphragm is still poor.
Claims (10)
1. a kind of anode sizing agent, including：
Positive active material；
Conductive agent；
Binder；And
N-Methyl pyrrolidone；
It is characterized in that,
The anode sizing agent further includes：Plasticizer；
The plasticizer is dissolved each other with N-Methyl pyrrolidone；
The plasticizer be at room temperature liquid, the plasticizer boiling point not less than 150 DEG C and the plasticizer flash-point not
Less than 110 DEG C；
Contain polar functional group in the molecular structure of the plasticizer, the polar functional group include-OH ,-COOH ,-(C=O)
One or more of O-；
The crystallinity for the glued membrane that the plasticizer is formed with Kynoar is less than the knot for the glued membrane that Kynoar itself is formed
Brilliant degree.
2. anode sizing agent according to claim 1, which is characterized in that the plasticizer includes polyethylene glycol, epoxy soybean
One or more of oil, tributyl citrate, tributyl 2-acetylcitrate.
3. anode sizing agent according to claim 1, which is characterized in that the binder includes Kynoar, described poly-
Vinylidene is selected from one or more of vinylidene fluoride homopolymer, vinylidene fluoride copolymers.
4. anode sizing agent according to claim 3, which is characterized in that the vinylidene fluoride copolymers are selected from inclined difluoro second
Alkene-hexafluoropropylene copolymer, vinylidene-tetrafluoroethylene-propylene terpolymer, biasfluoroethylene-hexafluoropropylene-tetrafluoroethene
One or more of terpolymer, vinylidene-chlorotrifluoroethylene.
5. anode sizing agent according to claim 1, which is characterized in that the quality of the plasticizer and the positive electrode active material
The ratio between matter, quality summation of conductive agent, binder and plasticizer are (0.5~5):100.
6. anode sizing agent according to claim 1, which is characterized in that the conductive agent be selected from conductive black, superconduction carbon black,
One or more of electrically conductive graphite, acetylene black, Ketjen black, graphene, carbon nanotube.
7. anode sizing agent according to claim 1, which is characterized in that the positive active material be selected from lithium and cobalt oxides,
In lithium nickel oxide, lithium manganese oxide, Li, Ni, Mn oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, LiFePO4
It is one or more of.
8. a kind of positive plate, including：
Plus plate current-collecting body；And
Positive diaphragm is arranged on the surface of the plus plate current-collecting body；
It is characterized in that,
The anode diaphragm is is formed by the anode sizing agent described in any one of claim 1-7.
9. a kind of energy storage device, which is characterized in that including positive plate according to claim 8.
10. energy storage device according to claim 9, which is characterized in that the energy storage device be selected from ultracapacitor, lithium from
Sub- secondary cell, sodium ion secondary battery.
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