CN108630864A - A kind of cathode and diaphragm integral structure and preparation method thereof and battery - Google Patents
A kind of cathode and diaphragm integral structure and preparation method thereof and battery Download PDFInfo
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- CN108630864A CN108630864A CN201710184319.8A CN201710184319A CN108630864A CN 108630864 A CN108630864 A CN 108630864A CN 201710184319 A CN201710184319 A CN 201710184319A CN 108630864 A CN108630864 A CN 108630864A
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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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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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
- 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
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
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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
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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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
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
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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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Abstract
The present invention provides a kind of cathode and diaphragm integral structure, including metal foil and the porous organic polymer membrane in the metal foil surface is set, the metal foil functions simultaneously as negative current collector and negative electrode active material, and the porous organic polymer membrane serves as diaphragm.The integral structure can effectively reduce the volume and weight of battery, simplify production process, increase the whole volume and energy density of battery, the high rate capability and high-temperature behavior for improving battery simultaneously solve the problems such as existing secondary cell production technology is complicated, early investment is big, battery safety is poor, energy density is low, design and assembly are difficult.The present invention also provides the preparation method of the cathode and diaphragm integral structure and include the battery of the integral structure.
Description
Technical field
The present invention relates to secondary battery technologies, more particularly to a kind of cathode and diaphragm integral structure and its preparation
Method and battery.
Background technology
Currently, commercial li-ion battery is mostly used graphite type material as negative material, however, since lithium ion is negative in graphite
Insertion site in the material of pole is limited, and theoretical specific capacity only has 372mAh g-1, to which the energy for limiting lithium ion battery is close
Degree, cannot meet the needs of novel consumer electronics product, electric vehicle, energy-accumulating power station etc..The diaphragm then porous poly- second of multiselect
Alkene/PP type diaphragm so that the heat resistance of battery is poor, is easy to happen thermal runaway, and then causes serious safety problem.For
Make diaphragm that there is enough intensity, there must be certain lower thickness limit, which limits further carrying for battery capacity
It is high.If simple reduction film thickness, it will cause the local strength of film insufficient, while form can be caused to lack at high temperature
It falls into, so, the reduction space of these film thicknesses is limited.
In addition, the production technology of existing secondary cell is relatively complicated, including positive and negative anodes batch mixing, coating, roll-in, film-making, weldering
Lug winds, enters shell, drying, fluid injection, standing, sealing, chemical conversion, partial volume, to factory, automation equipment, personnel
Proficiency is more demanding, and early investment is big.
Invention content
Can have in consideration of it, first aspect present invention provides a kind of cathode and diaphragm integral structure, the integrated design
Effect reduces the volume and weight of battery, simplifies production process, increases the whole volume and energy density of battery, while improving electricity
The high rate capability and high-temperature behavior in pond.
In a first aspect, the present invention provides a kind of cathode and diaphragm integral structure, including metal foil and setting are in institute
The porous organic polymer membrane of metal foil surface is stated, the metal foil functions simultaneously as negative current collector and negative electrode active material
Material, the porous organic polymer membrane serve as diaphragm.
In embodiment of the present invention, according to specific applicable cases, the hole organic polymer films can be formed in institute
The side surface for stating metal foil can also be the whole surface for being formed in the metal foil.When being formed in a side surface,
An electrode unit can be constituted with anode, be fabricated to button cell etc.；When being formed in whole surface, can be formed with anode multiple
The electrode unit of superposition is fabricated to takeup type commercial batteries etc..
In the cathode and diaphragm integral structure of the present invention, metal foil is anti-by alloying-removal alloying with lithium ion
It should realize battery charging and discharging.
The material of the metal foil includes in titanium, manganese, chromium, gallium, magnesium, vanadium, germanium, indium, aluminium, copper, iron, tin, nickel, zinc, lithium
Any one, or the alloy containing at least one above-mentioned metallic element.Some surface states of metal foil surface or suspension
Key can generate certain interaction with the organic polymer in porous organic polymer membrane, to have between the two
Certain active force.
The metal foil surface is provided with female pattern, and the porous organic polymer membrane part is set to the spill
In pattern, the porous organic polymer membrane is set to be combined with the metal foil closer.The concrete shape of the female pattern
It is not particularly limited, can be regular, can also be irregular.The depth of groove of the female pattern can be 0.1 μm of -5 μ
m。
The metal foil surface is modified with the organic matter of the functional group containing Shuan Xing, the organic matter of the functional group containing Shuan Xing with
Organic polymer in the porous organic polymer membrane makes the porous organic polymer membrane and institute by chemical interaction
Metal foil is stated to combine closely.The organic matter of the functional group containing Shuan Xing can be organo silane coupling agent, chromium complex coupling
Agent, titanate coupling agent etc..
The material of the porous organic polymer membrane includes polyethylene glycol oxide, polymethyl methacrylate, Kynoar-
Hexafluoropropene, polyoxypropylene, Pioloform, polyvinyl acetal, polyvinylpyrrolidone, sulfonylurea polymer, the polymerization of polyphenylsulfone sulfonic acid
Object, butadiene-styrene rubber, polybutadiene, polyvinyl chloride, polystyrene, acrylate, chitose acid, polyvinyl alcohol, gathers at polyethylene oxide
One kind in vinyl butyral, polyethylene glycol, polyoxyalkylene acrylate glycol ester, polyethylene, polypropylene, phosphate-based polymer
Or the blending of a variety of or any one of the above or several polymer, copolymerization, grafting, combization, hyperbranched or cross-linked network object.
The thickness of the porous organic polymer membrane is 5-100 μm.It can be further 20-60 μm.
In embodiment of the present invention, porous organic polymer membrane system by the way of hot pressing, blade coating, spin coating or roll-in
Standby or setting is in the metal foil surface.
Second aspect, the present invention provides the preparation methods of a kind of cathode and diaphragm integral structure, include the following steps：
Metal foil, the metal foil is taken to function simultaneously as negative current collector and negative electrode active material；
The slurry containing organic polymer or organic polymer precursor body is taken, by the slurry by the way of blade coating or spin coating
Coated in the metal foil surface, after cured molding, porous organic polymer membrane is obtained to get integrated to cathode and diaphragm
Change structure；
Or porous organic polymer membrane is directly taken, by the porous organic polymer membrane pressure by the way of hot pressing or roll-in
The metal foil surface is closed to get to cathode and diaphragm integral structure.
Wherein, the material of the metal foil include titanium, manganese, chromium, gallium, magnesium, vanadium, germanium, indium, aluminium, copper, iron, tin, nickel, zinc,
Any one in lithium, or the alloy containing at least one above-mentioned metallic element.
The slurry containing organic polymer includes organic polymer and solvent, and the solvent includes acetone, N-2- methyl
Pyrrolidones, tetrahydrofuran, toluene, chloroform, triethanolamine, hexamethylene, ether, methyl carbonate etc..
The organic polymer can be polyethylene glycol oxide, polymethyl methacrylate, Kynoar-hexafluoropropene,
Polyoxypropylene, Pioloform, polyvinyl acetal, polyvinylpyrrolidone, sulfonylurea polymer, polyphenylsulfone sulfonic acid polymer, polycyclic oxygen second
Alkane, butadiene-styrene rubber, polybutadiene, polyvinyl chloride, polystyrene, acrylate, chitose acid, polyvinyl alcohol, polyvinyl alcohol contracting fourth
It is one or more in aldehyde, polyethylene glycol, polyoxyalkylene acrylate glycol ester, polyethylene, polypropylene, phosphate-based polymer, or
The blending of any one of the above or several polymer, copolymerization, grafting, combization, hyperbranched or cross-linked network object.The organic polymer
Object presoma is the persursor material of above-mentioned organic polymer.
In the present invention, the thickness of the blade coating is 10-100 μm, and the speed of the spin coating is 10-10000rpm, spin coating
Time is 5-1200s.
In the present invention, the temperature of the hot pressing is 80-300 DEG C, and the pressure of hot pressing is 5-100Mpa, and the time of hot pressing is
The pressure of 10-1200s, roll-in are 50-150Mpa.
In order to make metal foil and porous organic polymer membrane preferably be combined together to form integral structure, the present invention
In, before preparing or the porous organic polymer membrane is set, female pattern first is set in the metal foil surface.Spill
The method that frosted, molding, laser ablation or chemical etching may be used in pattern is prepared.The concrete shape of the female pattern
It is not particularly limited, can be regular, can also be irregular.The depth of groove of the female pattern can be 0.1 μm of -5 μ
m。
Similarly, it in order to enhance the combination of metal foil and porous organic polymer membrane, in of the invention, preparing or is being arranged
Before the porous organic polymer membrane, the organic matter of the functional group containing Shuan Xing is first modified in the metal foil surface.Specific behaviour
As：The metal foil is immersed in the solution of organic matter of the functional group containing Shuan Xing, surface modification is completed.Certainly, this hair
It, also can be after female pattern be set, further in the metal foil surface modification for being provided with female pattern containing double property functions in bright
The organic matter of group.The organic matter of the functional group containing Shuan Xing can be organo silane coupling agent, chromium complex coupling agent, titanate esters
Coupling agent etc..
The third aspect, the present invention provides a kind of battery, including anode, electrolyte, and such as first aspect present invention institute
The cathode and diaphragm integral structure stated, the anode include plus plate current-collecting body and the anode being arranged on the plus plate current-collecting body
Active material layer, the anode active material layer include positive electrode active materials.The anode is close to the cathode and diaphragm one
Change the porous organic polymer membrane side of structure.
The positive electrode includes LiCoO2、LiMnO2、LiNiO2、LiFeO2、LiFePO4、(Li(NixCoyMn1-x-y)O2、
Li(NixCoyAl1-x-y)O2)、Na3V2(PO4)2F3、Na2FePO4F, one in natural graphite, expanded graphite, carbonaceous mesophase spherules
Kind is a variety of.
Electrolytic salt in the electrolyte includes one or more in lithium salts, sodium salt, aluminium salt, magnesium salts and zinc salt.
The preparation process of battery of the present invention may include steps of：
Cathode and diaphragm integral structure is made by the preparation method described in second aspect of the embodiment of the present invention in step 1；
Step 2 prepares anode：Positive electrode active materials, conductive agent, binder are scattered in suitably according to proper ratio
In solvent, it is configured to anode sizing agent；The anode sizing agent is coated on plus plate current-collecting body surface, required ruler is cut into after dry
It is very little, obtain anode；
Step 3 prepares electrolyte：Qs Electrolyte salt is weighed to be added in certain volume solvent, after being sufficiently stirred dissolving,
A certain amount of additive is added in reselection, stirs evenly rear spare.
Electrolytic salt described in step 3 is one or more of lithium salts, sodium salt, aluminium salt, magnesium salts, zinc salt etc.；Solvent is
One or more of esters, sulfone class, ethers, nitrile, olefines；Additive includes esters, sulfone class, ethers, nitrile or alkene
One or more of class organic additive.
The preparation of step 1-3 can while execute in any order.
Step 4, assembled battery：Under inert gas or anhydrous and oxygen-free environment, by the anode, cathode and diaphragm one
Body structure stacks gradually or is wound into battery core, and appropriate electrolyte is added dropwise, and is packaged in the battery case, completes battery
Assembling.
Implement the embodiment of the present invention, has the advantages that：
(1) cathode and diaphragm integral structure provided in an embodiment of the present invention, shortens negative ions between positive and negative anodes
Transmission range, transmission speed is improved, to alleviate polarization phenomena of the battery under high magnification so that battery is in high magnification
Under also have considerable capacity；
(2) cathode and diaphragm integral structure can effectively reduce the manufacturing technique requirent of battery, simplify technique, reduce production
Cost；Also it can be further reduced battery quality and volume, be conducive to the capacity and mass energy density that improve battery；
(3) cathode and diaphragm integral structure have excellent wettability power, imbibition rate, protect liquid rate, so as to enhance battery
To the utilization rate (and liquid-keeping property) of electrolyte.
(4) diaphragm ingredient thermostabilization in cathode and diaphragm integral structure is good, good mechanical property, to which battery can be improved
Security performance at high temperature, avoids the generation of thermal runaway, while increasing the mechanical strength of battery, the generation of dendrite inhibition.
Advantages of the present invention will be illustrated partly in the following description, and a part is apparent according to specification
, or can be through the embodiment of the present invention implementation and know.
Description of the drawings
Fig. 1 is the schematic diagram of cathode and diaphragm integral structure that the embodiment of the present invention 1 provides；
Fig. 2 is charging and discharging capacity and coulombic efficiency figure of the secondary cell of the embodiment of the present invention 1 under different multiplying；
Fig. 3 is charge-discharge performance figure of the secondary cell of the embodiment of the present invention 1 under 2C multiplying powers.
Specific implementation mode
As described below is the preferred embodiment of the embodiment of the present invention, it is noted that for the common skill of the art
For art personnel, under the premise of not departing from principle of the embodiment of the present invention, several improvements and modifications can also be made, these improvement
The protection domain of the embodiment of the present invention is also considered as with retouching.
Divide multiple embodiments that the embodiment of the present invention is further detailed below.
Embodiment 1
A kind of preparation method of cathode and diaphragm integral structure, includes the following steps：
(1) 0.75g Kynoar-hexafluoropropylene copolymer (PVDF-HFP) and 10mL acetone are packed into closed glass
In bottle, colourless transparent liquid is obtained after heating water bath (50 DEG C) and stirring (400r/min) 1h.Then, by the anhydrous of 2.5mL
Ethanol liquid is added dropwise in vial, and 0.5h is equally stirred under the conditions of 50 DEG C obtains required polymer solution；
(2) it is that 19 μm of aluminium foil makees negative electrode active material and negative current collector to take thickness, using 6000 mesh sand paper to it
Lateral roughening treatment is carried out, female pattern is formed in aluminium foil surface, is put into after being then cleaned by ultrasonic totally with acetone and alcohol
It is impregnated 2 minutes in organo silane coupling agent, is used in combination compressed air drying spare；
(3) method that step (1) resulting polymers solution scratches is applied directly to surface treated in step (2)
Aluminium foil surface is put into vacuum drying chamber (80 DEG C) dry 12h after coagulation forming to get to cathode and diaphragm integral structure.
Fig. 1 is the schematic diagram of cathode and diaphragm integral structure that the embodiment of the present invention 1 provides；In figure, 10 be aluminium foil, 11
It is porous organic polymer membrane for female pattern, 20.
The preparation of secondary cell
(1) anode is prepared：0.8g natural graphites, 0.1g conductive carbon blacks, 0.1g Kynoar are added to 4mL nitrogen
In methyl pyrrolidone solvent, it is fully ground acquisition uniform sizing material；Then slurry is evenly applied to aluminium foil surface, 80 DEG C of vacuum
Dry 12h, obtains anode；
(2) electrolyte is prepared：Prepare the LiPF of 4mol/L6Methyl ethyl carbonate ester solution (EMC), and the carbon of 2wt% is added
Sour vinylene (VC) is spare as electrolyte；
(3) secondary cell assembles：Argon gas protection glove box in, by the above-mentioned anode prepared, cathode and every
Film integral structure is discharged, is wound successively, and secondary cell assembling is completed using techniques such as electrolyte injection, sealings.
Electrochemical property test, charge-discharge velocity are carried out to the secondary cell of the embodiment of the present invention 1：2C (30min charge and discharges
Electricity), test temperature：25 DEG C, blanking voltage：3-4.95V, test result is as shown in Figures 2 and 3, and Fig. 2 is the embodiment of the present invention 1
Charging and discharging capacity and coulombic efficiency figure of the secondary cell under different multiplying；It would know that from Fig. 2, institute's acquisition secondary cell tool
There is excellent high rate performance.Under 10C charge-discharge velocities (charge and discharge in 6 minutes), capacity retention ratio still has 80% or more.
Fig. 3 is charge-discharge performance figure of the secondary cell of the embodiment of the present invention 1 under 2C multiplying powers.It would know that from Fig. 3,
Institute's acquisition secondary cell has excellent cyclical stability.Under 2C charge-discharge velocities (the charge and discharge time is 30min), 1000 times
Capacity can still keep 90% or more after cycle.
Embodiment 2-11
Embodiment 2-11 and the secondary cell preparation process of embodiment 1 remove the gold used in cathode and diaphragm integral structure
Belong to other than foil difference, other all steps and the material used are all identical, while being carried out to the secondary cell of embodiment 2-11
Electrochemical property test, and being compared with the performance of the embodiment of the present invention 1, metal foil used in embodiment 2-11 and its
Chemical property is referring specifically to table 1.
Table 1：The chemical property parameter list of the secondary cell of 1-11 of the embodiment of the present invention
As it can be seen from table 1 in the embodiment of the present invention, when cathode selects aluminium foil, battery specific capacity higher, cycle performance is more
It is good, energy density higher.
Embodiment 12-34
The secondary cell preparation process of embodiment 12-34 and embodiment 1, which is removed, prepares the positive-active used when anode
Material is with other than electrolyte difference, other all steps and the material used are all identical, while to the secondary electricity of embodiment 12-34
Pond carries out electrochemical property test, and is compared with the performance of the embodiment of the present invention 1, positive used in embodiment 12-34
Active material and its chemical property are referring specifically to table 2.
Table 2：The chemical property parameter list of the secondary cell of 12-34 of the embodiment of the present invention
From Table 2, it can be seen that in the embodiment of the present invention, positive electrode is graphite type material, LiCoO2、LiFePO4、Li
(NixCoyAl1-x-y)O2) etc. materials when, the secondary cell specific capacity higher assembled, energy density higher.
Embodiment 35-51
The secondary cell preparation process of embodiment 35-51 and embodiment 1, except making when preparing polymer solution in step (1)
Other than polymer material difference, other all steps and the material used are all identical.
Embodiment 52
With differing only in for embodiment 1, the method that polymer solution is prepared in step (1) is different, and what is be prepared is more
Pore polymer membrane material is different, and specifically, in the present embodiment, porous polymer membrane material is nitrile second cellulose-PVDF-HFP
Polymer blend, preparation process are：
(1) it is 1 weight ratio:1 nitrile second cellulose and Kynoar-hexafluoropropene (PVDF-HFP) is dissolved in acetone
In solvent, magnetic agitation makes two kinds of polymer fully dissolve at room temperature, and a certain amount of ethyl alcohol is then added, and stands 30min and sloughs
Bubble, you can obtain nitrile second cellulose-PVDF-HFP polymer blend precursor pulps；
(2) it is that 19 μm of aluminium foil makees negative electrode active material and negative current collector to take thickness, using 6000 mesh sand paper to it
Lateral roughening treatment is carried out, female pattern is formed in aluminium foil surface, is put into after being then cleaned by ultrasonic totally with acetone and alcohol
It is impregnated 2 minutes in organo silane coupling agent, is used in combination compressed air drying spare；
(3) by the method for nitrile second cellulose-PVDF-HFP polymer blend precursor pulps blade coating obtained by step (1)
It is applied directly to surface treated aluminium foil surface in step (2), is put into after coagulation forming in vacuum drying chamber (80 DEG C) dry
12h is to get to cathode and diaphragm integral structure.
Embodiment 53
With differing only in for embodiment 1, the method that polymer solution is prepared in step (1) is different, and what is be prepared is more
Pore polymer membrane material is different, and specifically, in the present embodiment, porous polymer membrane material is bis-epoxy polyethyleneglycol of end group-
The semi-interpenetrating network polymer of PVDF-HFP, preparation process are：
(1) in the acetone solvent that PVDF-HFP and polyethyleneimine (PEI) are sequentially added to certain mass according to a certain ratio,
Stirring 1h makes two kinds of polymer fully dissolve at room temperature, and bis-epoxy polyethyleneglycol of end group is then added, and stirring 1h forms uniformly molten
Liquid adds a certain amount of ethyl alcohol, stands 30min or more and sloughs bubble, obtains bis-epoxy polyethyleneglycol of end group-PVDF-HFP half
Interpenetrating net polymer precursor pulp；
(2) it is that 19 μm of aluminium foil makees negative electrode active material and negative current collector to take thickness, using 6000 mesh sand paper to it
Lateral roughening treatment is carried out, female pattern is formed in aluminium foil surface, is put into after being then cleaned by ultrasonic totally with acetone and alcohol
It is impregnated 2 minutes in organo silane coupling agent, is used in combination compressed air drying spare；
(3) by bis-epoxy polyethyleneglycol of end group-PVDF-HFP semi-interpenetrating network polymer precursor pulps obtained by step (1)
It is applied directly to surface treated aluminium foil surface in step (2) with the method for blade coating, vacuum drying chamber is put into after coagulation forming
Dry 12h is to get to cathode and diaphragm integral structure in (80 DEG C).
The secondary cell of embodiment 35-53 is subjected to electrochemical property test, and is carried out with the performance of the embodiment of the present invention 1
Compare, polymer material and battery performance used in embodiment 35-53 are specifically as shown in table 3.
Table 3：The chemical property parameter list of the secondary cell of 35-53 of the embodiment of the present invention
From table 3 it is observed that in the embodiment of the present invention, select Kynoar-hexafluoropropene as porous polymer
Membrane material, the battery specific capacity higher assembled, energy density higher, cycle performance are substantially improved.
Embodiment 54-56
The secondary cell preparation process of embodiment 54-56 and embodiment 1 is removed to prepare and is added dropwise when membrane for polymer solution
Other than absolute ethyl alcohol content difference, other all steps and the material used are all identical, while to the secondary electricity of embodiment 54-56
Pond carries out the electrochemical property test of battery, and is compared with the performance of the embodiment of the present invention 1, as a result referring to table 4.
Table 4：The chemical property parameter list of the secondary cell of 54-56 of the embodiment of the present invention
Embodiment 57-60
The secondary cell preparation process of embodiment 57-60 and embodiment 1 in addition to metal foil pretreatment mode difference,
His all steps and the material used are all identical, while carrying out electrochemical property test to the secondary cell of embodiment 57-60, and
It is compared with the performance of the embodiment of the present invention 1, as a result referring to table 5.
Table 5：The chemical property parameter list of the secondary cell of 57-60 of the embodiment of the present invention
As can be seen from Table 5, in the embodiment of the present invention, metal foil pretreatment mode is lateral roughening and organosilan
Effect is more preferable when coupling agent (2 minutes) is combined, the battery specific capacity higher assembled, energy density higher, cycle
Performance is substantially improved.
Embodiment 61-63
The secondary cell preparation process of embodiment 61-63 and embodiment 1 except apertured polymeric film set-up mode difference with
Outside, other all steps and the material used are all identical, while carrying out chemical property survey to the secondary cell of embodiment 61-63
Examination, and be compared with the performance of the embodiment of the present invention 1, as a result referring to table 6.
Table 6：The chemical property parameter list of the secondary cell of 61-63 of the embodiment of the present invention
As can be seen from Table 6, in the embodiment of the present invention, porous polymer film preparation is incorporated in by gold using blade coating mode
When belonging to foil surfaces, functional and saving production cost.
Cathode and diaphragm integral structure provided in an embodiment of the present invention can effectively reduce the volume and weight of battery, letter
Change production process, increase the whole volume and energy density of battery, while improving the high rate capability and high-temperature behavior of battery,
Solve that existing secondary cell production technology is complicated, early investment is big, battery safety is poor, energy density is low, design and assembly
The problems such as difficult.
Claims (13)
1. a kind of cathode and diaphragm integral structure, which is characterized in that including metal foil and be arranged in the metal foil table
The porous organic polymer membrane in face, the metal foil function simultaneously as negative current collector and negative electrode active material, and described porous have
Machine polymer film serves as diaphragm.
2. cathode as described in claim 1 and diaphragm integral structure, which is characterized in that the material of the metal foil includes
Any one in titanium, manganese, chromium, gallium, magnesium, vanadium, germanium, indium, aluminium, copper, iron, tin, nickel, zinc, lithium, or contain at least one above-mentioned gold
Belong to the alloy of element.
3. cathode as described in claim 1 and diaphragm integral structure, which is characterized in that the porous organic polymer membrane
Material includes polyethylene glycol oxide, polymethyl methacrylate, Kynoar-hexafluoropropene, polyoxypropylene, polyvinyl alcohol contracting
Aldehyde, polyvinylpyrrolidone, sulfonylurea polymer, polyphenylsulfone sulfonic acid polymer, polyethylene oxide, butadiene-styrene rubber, polybutadiene
Alkene, polyvinyl chloride, polystyrene, acrylate, chitose acid, polyvinyl alcohol, polyvinyl butyral, polyethylene glycol, polyethers third
One or more or any one of the above or several in olefin(e) acid glycol ester, polyethylene, polypropylene, phosphate-based polymer
The blending of polymer, copolymerization, grafting, combization, hyperbranched or cross-linked network object；The thickness of the porous organic polymer membrane is 5-
100μm。
4. cathode as described in claim 1 and diaphragm integral structure, which is characterized in that the metal foil surface is provided with
Female pattern, the porous organic polymer membrane part are set in the female pattern, to close with the metal foil
In conjunction with.
5. cathode as described in claim 1 and diaphragm integral structure, which is characterized in that the metal foil surface is modified with
The organic matter of the functional group containing Shuan Xing, the organic matter of the functional group containing Shuan Xing gather with organic in the porous organic polymer membrane
Object is closed by chemical interaction, the porous organic polymer membrane is made to combine closely with the metal foil.
6. cathode as claimed in claim 5 and diaphragm integral structure, which is characterized in that the functional group containing Shuan Xing it is organic
Object includes at least one of organo silane coupling agent, chromium complex coupling agent, titanate coupling agent.
7. cathode as described in claim 1 and diaphragm integral structure, which is characterized in that the porous organic polymer membrane is adopted
It is prepared or is arranged in the metal foil surface with the mode of hot pressing, blade coating, spin coating or roll-in.
8. the preparation method of a kind of cathode and diaphragm integral structure, which is characterized in that include the following steps：
Metal foil, the metal foil is taken to function simultaneously as negative current collector and negative electrode active material；
The slurry containing organic polymer or organic polymer precursor body is taken, the slurry is coated by the way of blade coating or spin coating
After the metal foil surface, cured molding, porous organic polymer membrane is obtained to get to cathode and diaphragm integration knot
Structure；
Or porous organic polymer membrane is directly taken, the porous organic polymer membrane is pressed to by the way of hot pressing or roll-in
The metal foil surface is to get to cathode and diaphragm integral structure.
9. the preparation method of cathode as claimed in claim 8 and diaphragm integral structure, which is characterized in that preparing or be arranged
Before the porous organic polymer membrane, first use the method for frosted, molding, laser ablation or chemical etching in the metal foil
Female pattern is arranged in piece surface.
10. the preparation method of cathode as claimed in claim 8 and diaphragm integral structure, which is characterized in that preparing or setting
Before setting the porous organic polymer membrane, the organic matter of the functional group containing Shuan Xing is first modified in the metal foil surface.
11. a kind of battery, which is characterized in that including anode, electrolyte, and such as claim 1-7 any one of them cathode
With diaphragm integral structure, the anode includes plus plate current-collecting body and the positive electrode active materials being arranged on the plus plate current-collecting body
Layer, the anode active material layer includes positive electrode active materials.
12. battery as claimed in claim 11, which is characterized in that the positive electrode includes LiCoO2、LiMnO2、LiNiO2、
LiFeO2、LiFePO4、(Li(NixCoyMn1-x-y)O2、Li(NixCoyAl1-x-y)O2)、Na3V2(PO4)2F3、Na2FePO4F, natural
It is one or more in graphite, expanded graphite, carbonaceous mesophase spherules.
13. battery as claimed in claim 11, which is characterized in that the electrolytic salt in the electrolyte include lithium salts, sodium salt,
It is one or more in aluminium salt, magnesium salts and zinc salt.
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Application publication date: 20181009 Assignee: REAL POWER INDUSTRIAL Ltd. Assignor: SHENZHEN INSTITUTES OF ADVANCED TECHNOLOGY Contract record no.: X2022980016102 Denomination of invention: An integrated structure of cathode and diaphragm, its preparation method and battery License type: Exclusive License Record date: 20220922 |
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