CN108630931A - 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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- CN108630931A CN108630931A CN201710184324.9A CN201710184324A CN108630931A CN 108630931 A CN108630931 A CN 108630931A CN 201710184324 A CN201710184324 A CN 201710184324A CN 108630931 A CN108630931 A CN 108630931A
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/46—Alloys based on magnesium or aluminium
- H01M4/463—Aluminium based
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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
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
- H01M4/662—Alloys
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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
- 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
- H01M50/431—Inorganic material
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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
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Abstract
The present invention provides a kind of cathode and diaphragm integral structure, including aluminum or aluminum alloy foil, and it is formed in the alumina layer on aluminum or aluminum alloy foil surface, the aluminum or aluminum alloy foil functions simultaneously as negative current collector and negative electrode active material, and the alumina layer serves as diaphragm.The integrated design 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 of battery are improved simultaneously, safety is improved, solves 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
In recent years, being continuously increased with population, people constantly increase the consumption of the energy and demand, find novel energy
Source supply mode and efficient energy storage mode become the active demand of today's society.Secondary cell, because it repeats charge and discharge
Use cost can be greatly lowered in electricity, and environmental pollution is small, and is widely used in various portable electronic devices.
Currently, commercial secondary cell uses graphite type material as cathode more, copper foil is as negative current collector, polyolefins
Material is as diaphragm.However, such battery structure is for improving the energy density of secondary lithium battery, simplifying production work
Skill reduces cost in the presence of obstruction.For example, relatively low (the 372mAh g of the theoretical specific capacity of graphite cathode-1), and compacted density is low, no
Conducive to the energy density of raising battery；Negative electrode active material needs are mutually compound with binder, conductive black etc., and are coated in copper foil
On collector, production technology is relatively complicated, and is easy to fall off between negative electrode active material and collector；The polyene used at this stage
The thermostabilization of hydrocarbon diaphragm material and mechanical performance are poor, are easy to happen thermal runaway and puncture phenomenon, to cause certain safety hidden
Suffer from.
Invention content
In consideration of it, the present invention provides a kind of cathode and diaphragm integral structure, which can effectively reduce electricity
The volume and weight in pond simplify production process, increase the whole volume and energy density of battery, while improving the high power of battery
Rate performance and high-temperature behavior improve safety.
Specifically, in a first aspect, the present invention provides a kind of cathode and diaphragm integral structure, including aluminum or aluminum alloy
Foil, and it is formed in the alumina layer on aluminum or aluminum alloy foil surface, the aluminum or aluminum alloy foil functions simultaneously as negative pole currect collecting
Body and negative electrode active material, the alumina layer serve as diaphragm.
In embodiment of the present invention, according to specific applicable cases, the alumina layer can be formed in the aluminium or
One side surface of alloy foil can also be the whole surface for being formed in the aluminum or aluminum alloy foil.When being formed in a side surface
When, 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
The electrode unit of multiple superpositions is fabricated to takeup type commercial batteries etc..
It is 10-3000nm that the alumina layer, which has porous structure, the porous aperture, and porosity is less than or equal to
85%.Further, the porous aperture is 200-1000nm, porosity 10%-85%.The porous structure of alumina layer
With aluminum or aluminum alloy foil alloying reaction occurs for the metal ion be conducive in electrolyte.
The thickness of the alumina layer is the 10%-200% of aluminum or aluminum alloy foil thickness；The thickness of the alumina layer is
5-50μm.Suitable alumina layer thickness can ensure good mechanical performance, prevent the generation for puncturing phenomenon, and ensure positive and negative
The electrical short of pole, ion conducting.
The thickness of the aluminum or aluminum alloy foil is 10-200 μm, and further, thickness can be 50-200 μm.Suitable thickness
It can guarantee its performance as negative current collector and negative electrode active material performance simultaneously.
The aluminum or aluminum alloy foil is the aluminum or aluminum alloy foil of densification, or is porous aluminum or aluminum alloy foil.When described
When aluminum or aluminum alloy foil is porous, the bulking effect of battery can be effectively relieved, improve cycle performance.The alloy foil can be
Aluminium-copper alloy foil, alumal foil, almag foil, alusil alloy foil etc..
The cathode and diaphragm integral structure that first aspect present invention provides, by by negative current collector, negative electrode active material
Material and diaphragm carry out integrated design, can significantly reduce the weight and volume of battery, are conducive to increase the active material in battery
Accounting improves battery energy density；Be conducive to simplify battery production technology, reduce cost；Alumina layer in structure play every
Film acts on, and has excellent mechanical strength, can effectively prevent thermal runaway and puncture the generation of phenomenon, improve battery safety；
When the integral structure is applied to battery system, metallic aluminium realizes cell reaction by alloying/removal alloying, relative to biography
Graphite material of uniting has more height ratio capacity.
Second aspect, the present invention provides the preparation methods of a kind of cathode and diaphragm integral structure, include the following steps：
Aluminum or aluminum alloy foil, the aluminum or aluminum alloy foil is taken to function simultaneously as negative current collector and negative electrode active material；
The aluminum or aluminum alloy foil one side coat organic polymer soln, formation organic polymer films to be solidified it
Afterwards, controllable oxidization is carried out to the another side of the aluminum or aluminum alloy foil by the way of anodic oxidation or plasma oxidation, made
The another side of the aluminum or aluminum alloy foil forms alumina layer；
The method calcined under an inert atmosphere again or use chemolysis, which is removed, is coated on the aluminum or aluminum alloy foil one side
The organic polymer films, obtain cathode and diaphragm integral structure.
Wherein, the thickness of the aluminum or aluminum alloy foil is 10-600 μm, and further, thickness can be 50-200 μm.It is described
Aluminum or aluminum alloy foil is the aluminum or aluminum alloy foil of densification, or is porous aluminum or aluminum alloy foil, the hole of aluminum or aluminum alloy foil
Rate is 0-85%.
The organic polymer soln includes one or more in following organic polymer：Polyacrylonitrile, polyvinylidene fluoride
Alkene, polyacrylic acid, polyurethane, polyvinyl butyral, polytetrafluoroethylene (PTFE), polyurethane, polyethylene, polypropylene, poly-methyl pyrrole
Alkanone, polyvinyl chloride, polyether sulfone, polyethylene glycol oxide, polymethyl methacrylate, Kynoar-hexafluoropropene, gather polysulfones
Oxypropylene, 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
Aldehyde, polyethylene glycol, polyoxyalkylene acrylate glycol ester, phosphate-based polymer.
Wherein, the organic solvent in the organic polymer soln includes methanol, ethyl alcohol, ethylene glycol, acetone, dimethyl methyl
Amide, propylene glycol monomethyl ether, propene carbonate, ethylene carbonate, dimethyl carbonate, dipropyl carbonate, ethyl propyl carbonic acid ester, carbonic acid are sub-
Vinyl acetate, carbonic acid second isopropyl ester, carbonic acid first butyl ester, dibutyl carbonate, ethyl butyl carbonate, methyl ethyl carbonate, diethyl carbonate,
It is one or more in gamma-butyrolacton and N-Methyl pyrrolidone；The mass concentration of the organic polymer soln is 0.1-
100mg/mL。
The anodic oxidation includes constant voltage anodic oxidation or constant current anode oxidation, the electricity of the constant voltage anodic oxidation
Pressure is 5~200V, can be further 10~40V；The electric current of the constant current anode oxidation is 0.01~6A cm-2, the anode
The time of oxidation is 0.1~240min, can be further 30~180min.
The anodic oxidation electrolyte is not particularly limited, and can use the sun of various well known suitable light metal materials
The electrolyte of pole oxidation.For example, the electrolyte can be the electrolyte of oxalates, phosphate or silicate systems；The phosphorus
The electrolyte of silicate system can be the aqueous solution containing phosphate and hydroxide；The electrolyte of the silicate systems can be with
For the aqueous solution containing silicate and hydroxide.The temperature of the anodic oxidation electrolyte is 0~40 DEG C, further may be used
It is 1~25 DEG C.
The gases used plasma oxidation is oxygen, and flow 10-300sccm, power 10-150W, the time is
1-360min, temperature are 25-400 DEG C.
The alumina layer can be the oxide layer of compact texture, can also be the porous hole with porous structure
Diameter is 10-3000nm, and porosity is less than or equal to 85%.When aluminum or aluminum alloy foil itself is compact texture, anodic oxidation is used
Mode, and control technological parameter, the alumina layer with porous structure, in such cases, alumina layer can be obtained
Porous aperture is about tens to hundreds of nanometers.And when aluminum or aluminum alloy foil itself has porous, using anodic oxidation and it is equal from
Daughter oxidation can obtain the alumina layer with porous structure, and porous size is differed with the pore size of aluminum or aluminum alloy foil substrate
Less.When aluminum or aluminum alloy foil itself have it is porous when, when coating organic polymer soln, make porous internal walls also attached last layer
Organic polymer soln.
It is calcined under the inert atmosphere, wherein inert atmosphere can be at least one of hydrogen, argon gas, nitrogen, calcining
Temperature can be 200-700 DEG C, can be further 300-650 DEG C；Calcination time can be 0.5-4 hours.The chemistry
The method of dissolving can be specifically that the aluminum or aluminum alloy foil after anodic oxidation is placed in the organic solvent under certain temperature
Reason a period of time, organic polymer films is made to dissolve.The organic solvent includes methanol, ethyl alcohol, ethylene glycol, acetone, dimethyl methyl
Amide, propylene glycol monomethyl ether, propene carbonate, ethylene carbonate, dimethyl carbonate, dipropyl carbonate, ethyl propyl carbonic acid ester, carbonic acid are sub-
Vinyl acetate, carbonic acid second isopropyl ester, carbonic acid first butyl ester, dibutyl carbonate, ethyl butyl carbonate, methyl ethyl carbonate, diethyl carbonate,
It is one or more in gamma-butyrolacton and N-Methyl pyrrolidone.The temperature can need to set according to different solvents.
The preparation method for the cathode and diaphragm integral structure that second aspect of the present invention provides, simple for process, raw material is easy to get,
It is environmental-friendly, suitable for commercially producing.
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 alumina layer 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, sylvite, calcium salt and magnesium salts.
The preparation process of the battery of the above-mentioned offer 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, sylvite, calcium salt and magnesium salts；Solvent is ester
One or more of class, sulfone class, ethers, nitrile, olefines；Additive includes esters, sulfone class, ethers, nitrile or olefines
One or more of 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.
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 structural schematic diagram of the porous aluminium foil of the embodiment of the present invention；
Fig. 2 is the structural schematic diagram of the cathode and diaphragm integral structure of the embodiment of the present invention.
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.
Embodiment 1
A kind of preparation method of cathode and diaphragm integral structure, includes the following steps：
(1) one block of sheet glass is taken, after being cleaned by ultrasonic 15min using acetone, is dried spare；Take porosity be 85% it is porous
Aluminium foil (as shown in Figure 1) after being respectively washed 10min using ethyl alcohol and acetone, dries spare.
(2) it weighs 50mg polyacrylonitrile (PAN) to be dissolved in 10mL dimethylformamides (DMF), is then heated to 50 DEG C, protect
5min or more is held, PAN is made to be completely dissolved, obtains polyacrylonitrile solution；Take the above-mentioned polyacrylonitrile solution drop coatings of 500 μ L in glass base
On bottom, after solution is evenly dispersed, porous aluminium foil is placed on above, allow the porous aluminium foil of polyacrylonitrile solution homogeneous immersion (only
Expose upper surface), after drying, then sheet glass is put together together with porous aluminium foil and is heated on the heaters, heating temperature be 70~
80 DEG C, after polyacrylonitrile solution is formed by curing polyacrylonitrile film, sheet glass is removed, a side surface is obtained and is coated with polyacrylonitrile film
Porous aluminium foil；
(3) at 4 DEG C, electrolyte (concentration 0.3mol/L) is done with oxalic acid aqueous solution, a side surface is coated with poly- third
The porous aluminium foil of alkene nitrile film is anode, and graphite is that cathode carries out constant voltage anodic oxidation, and the another side of the porous aluminium foil is made to send out
Raw oxidation generates alumina layer, and the voltage of anodic oxidation is 20V, time 60min.
(4) under hydrogen-argon-mixed atmosphere, the porous aluminium foil after anodic oxidation is heat-treated 3h at 650 DEG C, is removed
Polyacrylonitrile film layer obtains cathode and diaphragm integral structure.
Fig. 2 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 alumina layer for porous hole, 20.
The preparation of secondary cell
(1) anode is prepared：0.4g cobalt acid lithiums, 0.05g conductive carbon blacks, 0.05g Kynoar are added to 3mL 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.The disk that a diameter of 10mm is cut into dry the electrode obtained piece is placed in glove box spare as anode；
(2) cathode and diaphragm integral structure that the embodiment of the present invention 1 is prepared are cut into the circle of a diameter of 12mm
Piece is placed in glove box spare as battery cathode；
(3) electrolyte is prepared：1mol/L lithium hexafluoro phosphates-ethylene carbonate (EC) is prepared in glove box：Carbonic acid diformazan
Ester (DMC)：Methyl ethyl carbonate (EMC) (v/v/v=1:1:1), and the vinylene carbonate of 5wt% is added as additive conduct
Electrolyte is spare；
(4) secondary cell assembles：In the glove box of argon gas protection, by the above-mentioned anode prepared, battery cathode
It discharges, wind successively, secondary cell assembling is completed using techniques such as electrolyte injection, sealings.
Embodiment 2-11
Compared with Example 1, embodiment 2-11 is differed only in, will in step (1) and step (2) in embodiment 1
The anodized condition of material and treatment conditions and step (3), the calcining post-treatment condition in step (4) are substituted for
As shown in Table 1 and Table 2, other operations are same as Example 1.
The step of 1 embodiment 2-11 of table (1) and the material in step (2) and treatment conditions
The anodized and post-treatment condition of 2 embodiment 2-11 of table
It is prepared by secondary cell
(1) anode is prepared：0.4g artificial graphites, 0.05g conductive carbon blacks, 0.05g polytetrafluoroethylene (PTFE) are added to 3mL
In N-methyl pyrrolidinone solvent, it is fully ground acquisition uniform sizing material；Then slurry is evenly applied to aluminium foil surface, 80 DEG C true
The dry 12h of sky.The disk that a diameter of 10mm is cut into dry the electrode obtained piece is placed in glove box standby as anode
With；
(2) cathode and diaphragm integral structure that the embodiment of the present invention 2 is prepared are cut into the circle of a diameter of 12mm
Piece is placed in glove box spare as battery cathode；
(3) electrolyte is prepared：4mol/L lithium hexafluoro phosphates methyl ethyl carbonate (EMC) is prepared in glove box, is added
The vinylene carbonate ester additive of 5wt%, it is spare as electrolyte；
(4) secondary cell assembles：In the glove box of argon gas protection, by the above-mentioned anode prepared, battery cathode
It discharges, wind successively, secondary cell assembling is completed using techniques such as electrolyte injection, sealings.
It is prepared by secondary cell
(1) anode is prepared：0.4g LiFePO4s, 0.05g electrically conductive graphites, 0.05g polytetrafluoroethylene (PTFE) are added to 3mL
In N-methyl pyrrolidinone solvent, it is fully ground acquisition uniform sizing material；Then slurry is evenly applied to aluminium foil surface, 80 DEG C true
The dry 12h of sky.The disk that a diameter of 10mm is cut into dry the electrode obtained piece is placed in glove box standby as anode
With；
(2) cathode and diaphragm integral structure that the embodiment of the present invention 3 is prepared are cut into the circle of a diameter of 12mm
Piece is placed in glove box spare as battery cathode；
(3) electrolyte is prepared：1mol/L lithium hexafluoro phosphates-ethylene carbonate (EC) is prepared in glove box：Carbonic acid diethyl
Ester (DEC) (v/v=1:1), and the vinylene carbonate ester additive of 5wt% is added, it is spare as electrolyte；
(4) secondary cell assembles：In the glove box of argon gas protection, by the above-mentioned anode prepared, battery cathode
It discharges, wind successively, secondary cell assembling is completed using techniques such as electrolyte injection, sealings.
Embodiment 12-21
Respectively by the calcining or change in the oxidation processes condition of (3) the step of 2-11 of the embodiment of the present invention and step (4)
The post-treatment condition for learning dissolving is substituted for as shown in table 3, obtains 12-21 of the embodiment of the present invention.
Plasma oxidation processing in 3 embodiment 12-21 of table and post-treatment condition
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 (12)
1. a kind of cathode and diaphragm integral structure, which is characterized in that including aluminum or aluminum alloy foil, and be formed in the aluminium or
The alumina layer on alloy foil surface, the aluminum or aluminum alloy foil functions simultaneously as negative current collector and negative electrode active material, described
Alumina layer serves as diaphragm.
2. cathode as described in claim 1 and diaphragm integral structure, which is characterized in that the alumina layer has porous knot
Structure, the porous aperture are 10-3000nm, and porosity is less than or equal to 85%.
3. cathode as described in claim 1 and diaphragm integral structure, which is characterized in that the thickness of the alumina layer is 5-
50μm；The thickness of the aluminum or aluminum alloy foil is 10-200 μm.
4. cathode as described in claim 1 and diaphragm integral structure, which is characterized in that the thickness of the alumina layer is institute
State the 10%-200% of aluminum or aluminum alloy foil thickness.
5. cathode as described in claim 1 and diaphragm integral structure, which is characterized in that the aluminum or aluminum alloy foil is densification
Aluminum or aluminum alloy foil, or be porous aluminum or aluminum alloy foil.
6. the preparation method of a kind of cathode and diaphragm integral structure, which is characterized in that include the following steps：
Aluminum or aluminum alloy foil, the aluminum or aluminum alloy foil is taken to function simultaneously as negative current collector and negative electrode active material；
After the one side coating organic polymer soln of the aluminum or aluminum alloy foil, formation organic polymer films to be solidified, adopt
Controllable oxidization is carried out to the another side of the aluminum or aluminum alloy foil with the mode of anodic oxidation or plasma oxidation, makes the aluminium
Or the another side of alloy foil forms alumina layer；
It calcines under an inert atmosphere again or the institute for being coated on the aluminum or aluminum alloy foil one side is removed using the method for chemolysis
Organic polymer films are stated, cathode and diaphragm integral structure are obtained.
7. the preparation method of cathode as claimed in claim 6 and diaphragm integral structure, which is characterized in that the organic polymer
Object solution includes one or more in following organic polymer：Polyacrylonitrile, polyacrylic acid, polyurethane, gathers Kynoar
Vinyl butyral, polytetrafluoroethylene (PTFE), polyurethane, polyethylene, polypropylene, poly-methyl pyrrole alkanone, polyvinyl chloride, gather polysulfones
Ether sulfone, polymethyl methacrylate, Kynoar-hexafluoropropene, polyoxypropylene, Pioloform, polyvinyl acetal, is gathered polyethylene glycol oxide
Vinylpyrrolidone, polyphenylsulfone sulfonic acid polymer, polyethylene oxide, butadiene-styrene rubber, polybutadiene, gathers sulfonylurea polymer
Vinyl chloride, polystyrene, acrylate, chitose acid, polyvinyl alcohol, polyvinyl butyral, polyethylene glycol, polyoxyalkylene acrylate second
Diol ester, phosphate-based polymer.
8. the preparation method of cathode as claimed in claim 6 and diaphragm integral structure, which is characterized in that the organic polymer
Organic solvent in object solution includes methanol, ethyl alcohol, ethylene glycol, acetone, dimethylformamide, propylene glycol monomethyl ether, propylene carbonate
Fat, ethylene carbonate, dimethyl carbonate, dipropyl carbonate, ethyl propyl carbonic acid ester, vinylene carbonate, carbonic acid second isopropyl ester, carbonic acid
First butyl ester, dibutyl carbonate, ethyl butyl carbonate, methyl ethyl carbonate, diethyl carbonate, gamma-butyrolacton and N-Methyl pyrrolidone
In it is one or more；The mass concentration of the organic polymer soln is 0.1-100mg/mL.
9. the preparation method of cathode as claimed in claim 6 and diaphragm integral structure, which is characterized in that the anodic oxidation
Including constant voltage anodic oxidation or constant current anode oxidation, the voltage of the constant voltage anodic oxidation is 5~200V, the permanent electricity
The electric current for flowing anodic oxidation is 0.01~6A cm-2, the time of the anodic oxidation is 0.1~240min, the anodic oxidation electricity
The temperature for solving liquid is 0~40 DEG C.
10. the preparation method of cathode as claimed in claim 6 and diaphragm integral structure, which is characterized in that the plasma
Gases used body oxidation is oxygen, flow 10-300sccm, power 10-150W, time 1-360min, temperature 25-
400℃。
11. a kind of battery, which is characterized in that including anode, electrolyte and cathode as described in any one in claim 1-5
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 electrolytic salt in the electrolyte include lithium salts, sodium salt,
It is one or more in sylvite, calcium salt and magnesium salts.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710184324.9A CN108630931A (en) | 2017-03-24 | 2017-03-24 | A kind of cathode and diaphragm integral structure and preparation method thereof and battery |
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| CN201710184324.9A CN108630931A (en) | 2017-03-24 | 2017-03-24 | A kind of cathode and diaphragm integral structure and preparation method thereof and battery |
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| CN201710184324.9A Pending CN108630931A (en) | 2017-03-24 | 2017-03-24 | A kind of cathode and diaphragm integral structure and preparation method thereof and battery |
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| TWI834035B (en) * | 2020-05-01 | 2024-03-01 | 日商大金工業股份有限公司 | Complexes, polymer electrolytes, electrochemical devices, polymer-based solid-state batteries and actuators |
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