CN104993150B - A kind of flexible device and preparation method thereof - Google Patents
A kind of flexible device and preparation method thereof Download PDFInfo
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- CN104993150B CN104993150B CN201510394861.7A CN201510394861A CN104993150B CN 104993150 B CN104993150 B CN 104993150B CN 201510394861 A CN201510394861 A CN 201510394861A CN 104993150 B CN104993150 B CN 104993150B
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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
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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
- H01M10/04—Construction or manufacture in general
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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
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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
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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
- H01M4/665—Composites
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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
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention belongs to flexible device technical field, in particular to a kind of flexible device：It is made of including a piece of positive plate, a piece of negative electrode tab and isolation film, negative electrode tab negative electrode active material and negative current collector；Negative current collector is made of porous structure layer and base layer；Porous structure layer includes pore structure area and non-porose area, and the volume of pore structure area and non-porose area is respectively V1, V2, and V1/ (V1+V2) >=10%；Negative electrode active material is distributed in the pore structure of porous structure layer or the surface of the non-porose area of porous structure layer, the quality for being distributed in the active material in the pore structure of porous structure layer is W1, the quality of the active material on the non-porose area surface of porous structure layer is distributed in as W2, and W1/ (W1+W2) >=10%.The present invention uses porous current collector, can increase the bonding force between collector and active material, it is ensured that interface closely bonds flexible device in the process of bending；Therefore the flexible device prepared has more excellent flexibility and chemical property.
Description
Technical field
The invention belongs to flexible device technical field, in particular to a kind of flexible device and preparation method thereof.
Background technique
1991, it was lithium ion that Sony Corporation of Japan's creativeness, which uses Carbon Materials as lithium ion battery anode material,
Field of batteries brings revolutionary variation；Since then, lithium ion battery technology grow rapidly, mobile phone, video camera,
It is largely used above laptop and other portable electronics.Lithium ion battery has many advantages, such as, such as voltage is high, body
Product is small, light weight, memory-less effect higher than ability, pollution-free, self discharge is small, has extended cycle life, and is 21st century ideal
Movable electrical appliances power supply, electric car power supply and electricity storage station electrical storage device.
But as electronic device develops towards personalized direction, a large amount of creativeness electronic products emerge in large numbers rapidly：Such as intelligence
The wearable devices such as energy wrist-watch, intelligent glasses, Intelligent bracelet occur in succession within a few years time and obtain the majority of consumers
Approval.Different from conditional electronic product, this electronic product has many characteristics, such as that shape is irregular, flexible, therefore to these electricity
The power supply part (i.e. battery) of sub- product is put forward new requirements：It is irregular, flexible etc..
For flexible device, in bending process back and forth, device inside interface will be by stern challenge；And electrochemistry
Device, interfacial reaction are to influence one of the deciding factor of its performance；Therefore to guarantee that flexible device has excellent electrochemistry
Performance, it is necessary to ensure that the device has excellent interface cohesive force.
A kind of flexible battery is disclosed in the U.S. Patent Application Publication No. 2013/0171490A1 that July 4 in 2013 announces
Upper and lower adhesion layer by upper and lower lamination by a series of battery-arrangements, and is bonded by the adhesive between battery and makes electricity by group
Pond isolation, to prepare flexible battery group.But the flexible battery group of this design bending when, due to top layers and bottom layer
Rigid stronger, affected by force, the bending degree and fatigue resistance of flexible battery group are very restricted, and influence flexible electrical
The performance of pond group performance；After certain bending angle and number of bends, adhesive strength can decline binder, lead to its fixing
It is deteriorated, and is being easy to produce fatigue since active force is inconsistent with adhesive free region similar in binder, to flexible battery group
Security performance it is risky.And this method needs to control the adhesive strength of adhesive and uniform, the amount of each region usage amount
What is produced is difficult.
In view of this, it is necessory to provide a kind of new flexible device, so that it is with excellent interface cohesive force, even if
It is still closely bonded after repeatedly bending, to prepare the flexible device of function admirable.
Summary of the invention
It is an object of the invention to：In view of the deficiencies of the prior art, a kind of electrochemical energy storing device provided：Including one
Piece positive plate, a piece of negative electrode tab and isolation film, the negative electrode tab are made of negative electrode active material and negative current collector；The cathode
Collector is made of porous structure layer and base layer, and the porous structure layer is attached to described matrix layer surface；The porous knot
Structure floor includes pore structure area and non-porose area, and the volume of the pore structure area and non-porose area is respectively V1, V2, and V1/ (V1+V2) >=
10%, contain enough holes in collector at this time, provides the space of storage active material；The negative electrode active material distribution
In the pore structure of the porous structure layer or the surface of the non-porose area of the porous structure layer, it is distributed in the porous structure layer
Pore structure in active material quality be W1, be distributed in the matter of the active material on the non-porose area surface of the porous structure layer
Measuring is W2, and W1/ (W1+W2) >=10%, at this time in the hole of the filling of the active substance part or whole porous current collector.
The present invention uses porous current collector, so that active material is wholly or partially embedded into the pore structure of porous current collector, to increase
Bonding force between collector and active material, it is ensured that interface closely bonds flexible device in the process of bending；Therefore it prepares
The flexible device come has more excellent flexibility and chemical property.
In order to achieve the above object, the present invention adopts the following technical scheme that：
A kind of flexible device, including a piece of positive plate, a piece of negative electrode tab and isolation film, the negative electrode tab is by negative electrode active material
Matter and negative current collector composition, it is characterised in that：
The negative current collector is made of porous structure layer and base layer, and the porous structure layer is attached to the base layer
Surface；
The porous structure layer includes pore structure area and non-porose area, and the volume of the pore structure area and non-porose area is respectively
V1, V2, and V1/ (V1+V2) >=10% contain enough holes at this time in collector, provide the space of storage active material；
The negative electrode active material is distributed in the pore structure of the porous structure layer or the non-hole of the porous structure layer
The surface in area, the quality for being distributed in the active material in the pore structure of the porous structure layer is W1, is distributed in the porous knot
The quality of the active material on the non-porose area surface of structure layer is W2, and W1/ (W1+W2) >=10%, at this time active substance part or complete
In the hole of the filling porous current collector in portion.
As a kind of improvement of flexible device of the present invention, the base layer has both conductive capability and water proof ability is metal list
At least one of matter, metal and metal alloy, metal and non-metal alloy, or be metal simple-substance or its alloy and other materials
Expect the composite material formed, and the base layer with a thickness of h, and h is greater than or equal to 1 μm, and collector is sufficiently thick, just with
To the hole with certain depth, it to be used for carrying active substance.
As a kind of improvement of flexible device of the present invention, the porous structure layer of the collector with a thickness of a, and 5 μm≤a
≤ 1000 μm, when porous structure layer thickness is excessive, it will increase ion diffusion path, so that the high rate performance of battery is deteriorated；It is described
The hole equivalent diameter of porous structure structure sheaf is that (equivalent bore dia refers to d when hole area is converted into an area of a circle, the circle
Diameter), and 0.1 μm≤d≤2cm, equivalent diameter is too small, can not fill enough active materials, and equivalent diameter is excessive, can not
Adequately show pore structure to the fixed function of active material, and will affect the electronic conductance of electrode；The porous structure layer
Pore wall thickness is b, and 0.01 μm≤b≤1cm；The hole length of the porous structure layer is L, and L≤4a, when hole depth is excessive,
The ion transmission path for being filled in active material in pore structure must be increased, to influence the high rate performance of battery；It is described porous
Structure sheaf is in the alloy and conducting polymer of alloy, metal and nonmetallic formation that metal simple-substance, metal and metal are formed
At least one, or the composite material formed for metal simple-substance, alloy, conducting polymer and other materials.
As a kind of improvement of flexible device of the present invention, 10 μm≤h≤100 μm, 20 μm≤a≤500 μm, 0.6 μm≤d≤
1cm, 0.05 μm≤b≤10mm, L≤2a；The hole shape of the porous structure layer is circle, ellipse, polygon, irregular shape
At least one of shape (hole that such as line segment and camber line are constituted).
As a kind of improvement of flexible device of the present invention, V1/ (V1+V2) >=50%；W1/ (W1+W2) >=50%.
As a kind of improvement of flexible device of the present invention, also contain conductive agent or/and bonding in the negative electrode active material
Agent；The porous structure layer has conductive capability, and the hole in the pore structure area runs through the entire porous structure layer；It is described
Be provided with conductive adhesion layer between porous structure layer and the base layer, and the conductive adhesion layer with a thickness of c, c≤1 μm.
As a kind of improvement of flexible device of the present invention, the metal include Mg, Ca, Sr, Ba, Ra, Al, Ga, In, Ge,
Sn、Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Ru、Rh、Pd、Ag、Cd、La、W、Pt、Au、Ce、Pr、
At least one of Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu；It is described it is nonmetallic include H, B, C, N, O, Si, P, S,
At least one of As, Se, Te, F, Cl, Br, I；The other materials is polymer composite, the polymer composite
The organic matter for being the molecular weight that is formed by the nonmetalloid 200 or more, including polypyrrole (PPy), polyaniline (PANi),
At least one in polyacrylonitrile (PAN), Polyglycolic acid fibre (PEDOT), polyethylene oxide (PEO) and polyethylene glycol (PEG)
Kind.
As a kind of improvement of flexible device of the present invention, the conducting polymer includes polythiophene and its derivative, poly- pyrrole
It coughs up and its at least one of derivative, Polyaniline and its derivative, polyacetylene, conducting resinl.
As a kind of improvement of flexible device of the present invention, the negative electrode active material include carbon material (graphite, disordered carbon),
Carbon compound (B~C~N series, C~Si~O series), non-carbon material (metal oxide, lithium~transition metal nitride,
At least one of lithium alloy)；The conductive agent includes conductive carbon black, super conductive carbon, carbon nanotube, Ketjen black, graphene
At least one of；The bonding agent include copolymer tetrafluoroethylene, equal polytetrafluoroethylene (PTFE), butadiene-styrene rubber, sodium carboxymethylcellulose,
At least one of polyacrylic acid, polypropylene cyanogen, polyvinyl alcohol, polyolefin, Viton, Polyurethane.
The invention also includes a kind of preparation methods of flexible device, mainly include the following steps：
Step 1, prepared by porous current collector：Porous structure layer is prepared, substrate surface is arranged in, so that porous structure layer adheres to
In substrate surface and electronic conduction, porous current collector is obtained；
Step 2, prepared by negative electrode tab：Negative electrode active material is arranged in the porous structure layer of porous current collector described in step 1
Side obtains negative electrode tab；
Step 3, flexible device assembles：Above-mentioned negative electrode tab and isolation film, positive plate are assembled, chemical conversion, shaping obtain flexibility
Device.
A kind of improvement of preparation method as flexible device of the present invention, which is characterized in that porous structure described in step 1
Layer is that directly preparation (just having formed porous structure during collector is prepared and formed) obtains porous structure layer or non-porous
Porous structure layer is prepared by etching in material；It is described etching include laser ablation, chemical etching, quantum bombardment at least
It is a kind of；The collector of positive plate described in step 3 can be porous current collector.
In addition, in order to increase flexible device wear resistance of the present invention, it can also be in the afflux body surface as encapsulating material
Layer increases one layer of polymeric layer, such as polyethylene, nylon layer, while the protective layer can also play the purpose of isolation electronics.
Compared with prior art, flexible device of the present invention and preparation method thereof has the following advantages that：
1. using the hole storage section negative electrode active material of porous current collector, it is possible to reduce coated on collection liquid surface
Active matter quality increases the adhesive force of surface covering and collector to reduce surface reactive material coating layer thickness；
2. use porous current collector, the contact area of electrode coating and collector can be increased, thus increase collector with
Bonding force between coating；
3. using porous current collector, the active material composition one of the active material and afflux surface layer in hole is organic whole
Falcon fourth of the twelve Earthly Branches structure is constituted between body, with collector, can greatly increase the adhesive strength between two kinds；
4. when preparing porous layer, preparation process is very simple since the porous current collector is divided into porous structure layer and base layer
Single, obtained hole uniformity is good；And base layer can play a dual role of battery packaging material and collector, barrier aqueous vapor into
Electronic conductance is carried out while entering inside battery and electronics is collected；Two kinds it is compound after collector have more excellent performance.
Specific embodiment
The present invention and its advantages are described in detail With reference to embodiment, but embodiment party of the invention
Formula is without being limited thereto.
Comparative example 1
Collector preparation：Select the copper foil with a thickness of 100 μm stand-by for collector.
Negative electrode tab preparation：With silicon-carbon compound (silicone content 30%), PVDF is bonding agent, Supper-P is conductive agent
(three's mass ratio is 94:3:3), NMP is that solvent configures slurry；It is coated in a surface of above-mentioned collector later, dry,
It is cold-pressed, cuts into monolithic (being all around empty foil area, centre is coating region) for use.
Battery assembly：Positive plate (single side coating is all around empty foil area, and centre is coating region), isolation film (are contained
Pvdf coating) cut into the size to match with above-mentioned positive plate；Drying, then spray electrolyte on positive coating and infiltrated
Positive plate afterwards；Negative current collector surrounding empty foil (coating is ipsilateral) area arrange adhesive layer, according to negative electrode tab, isolation film,
The mode of positive plate stacks (positive and negative anodes active matter is towards isolation film), hot later compound so that positive, isolation film, cathode are close
Bonding, the adhesive layer being simutaneously arranged in negative current collector surrounding closely bonds positive/negative plate together, and plays sealing surrounding
Purpose；Flexible device is being obtained by chemical conversion, shaping.
Embodiment 1
The preparation of porous current collector：Select the copper foil with a thickness of 1 μm as base layer；The copper foil with a thickness of 100 μm is selected,
Later by the way of laser boring, carrying out punching to the copper foil to obtain hole shape is circle, bore dia is 2 μm, Kong Jian
Away from (two bore edges) be 1 μm, hole depth is 100 μm of hole, to obtain the porous structure layer of porous current collector；It will be above-mentioned more
Pore structure layer and collective layer are cut, and are adhered on base layer using conductive rubber cement porous structure layer later and are obtained porous current collector and wait for
With；
Negative electrode tab preparation：With silicon-carbon compound (silicone content 30%) be negative electrode active material, PVDF be bonding agent,
Supper-P is that (three's mass ratio is 94 to conductive agent:3:3), NMP is that solvent configures slurry；It is coated in above-mentioned porous collection later
The surface (applied thickness being controlled when coating, so that W1/ (W1+W2)=50%) that fluid contains pore structure side, dry, be cold-pressed,
It is stand-by to cut into monolithic (being all around empty foil area, centre is coating region).
Battery assembly：With comparative example 1；
Embodiment 2
Difference from Example 1 is, includes the following steps：
The preparation of porous current collector：Select the copper foil with a thickness of 10 μm as base layer.
Remaining is same as Example 1, repeats no more.
Embodiment 3
Difference from Example 1 is, includes the following steps：
The preparation of porous current collector：Select the copper foil with a thickness of 15 μm as base layer；Select the copper with a thickness of 100 μm
Foil, later by the way of laser boring, carrying out punching to the copper foil to obtain hole shape is circle, bore dia is 1 μm, hole
Spacing (two bore edges) is 2.8 μm, hole depth is 100 μm of hole, to obtain the porous structure layer of porous current collector；It will be upper
It states porous structure layer to cut with collective layer, is adhered on base layer using conductive rubber cement porous structure layer obtains porous afflux later
Body is stand-by；
Negative electrode tab preparation：With silicon-carbon compound (silicone content 30%) be negative electrode active material, PVDF be bonding agent,
Supper-P is that (three's mass ratio is 94 to conductive agent:3:3), NMP is that solvent configures slurry；It is coated in above-mentioned porous collection later
The surface (applied thickness being controlled when coating, so that W1/ (W1+W2)=10%) that fluid contains pore structure side, dry, be cold-pressed,
It is stand-by to cut into monolithic (being all around empty foil area, centre is coating region).
Remaining is same as Example 1, repeats no more.
Embodiment 4
Difference from Example 1 is, includes the following steps：
The preparation of porous current collector：Select the copper foil with a thickness of 20 μm as base layer；Select the copper with a thickness of 150 μm
Foil, later by the way of laser boring, punching is carried out to the copper foil to obtain hole shape be it is round, bore dia is 0.1 μm,
Pitch of holes (two bore edges) is 0.05 μm, hole depth is 150 μm of hole, to obtain the porous structure layer of porous current collector；
By above-mentioned porous structure layer and collective layer cut, be adhered on base layer using conductive rubber cement porous structure layer later obtain it is porous
Collector is stand-by；
Negative electrode tab preparation：Using silicon as negative electrode active material, silicon nanoparticle is inserted in the pore structure of porous current collector, this
When, active material silicon is all restricted in the pore structure of porous current collector (i.e. W1/ (W1+W2)=100%), is taken out after cooling
Obtain positive plate；
Remaining is same as Example 1, repeats no more.
Embodiment 5
Difference from Example 4 is, includes the following steps：
The preparation of porous current collector：In porous structure layer, bore dia is 0.6 μm, and pitch of holes (two bore edges) is 0.05 μm
Remaining is same as Example 1, repeats no more.
Embodiment 6
Difference from Example 4 is, includes the following steps：
The preparation of porous current collector：In porous structure layer, bore dia is 2 μm, and pitch of holes (two bore edges) is 0.05 μm；
Remaining is same as Example 4, repeats no more.
Embodiment 7
The preparation of porous current collector：Select the copper foil with a thickness of 100 μm as base layer；Select the copper with a thickness of 1000 μm
Foil, later by the way of laser boring, chemical attack, it is rectangular, hole for carrying out punching to the copper foil to obtain hole shape
Equivalent diameter is 2cm, and pitch of holes (two bore edges) obtains the porous structure layer of porous current collector for 1cm's；It will be above-mentioned porous
Structure sheaf and collective layer are cut, and are adhered on base layer using conductive rubber cement porous structure layer later and are obtained porous current collector and wait for
With obtained hole depth is 1500 μm at this time；
Negative electrode tab preparation：Using lithium titanate as negative electrode active material, PVDF is bonding agent, Supper-P is conductive agent (three
Mass ratio is 94:3:3), NMP is that solvent configures slurry；Contain pore structure side coated in above-mentioned porous current collector later
Surface (controls applied thickness, so that W1/ (W1+W2)=90%) when coating, drying, be cold-pressed, cutting into monolithic (is all around sky
Foil area, centre are coating region) it is stand-by.
Battery assembly：With comparative example 1；
Embodiment 8
Difference from Example 7 is, includes the following steps：
The preparation of porous current collector：Select the copper foil with a thickness of 100 μm as base layer；Select the copper with a thickness of 300 μm
Foil, later by the way of laser boring, chemical attack, it is rectangular, hole for carrying out punching to the copper foil to obtain hole shape
Equivalent diameter is 1cm, and pitch of holes (two bore edges) is the porous structure layer of 10mm；Above-mentioned porous structure layer and collective's layer are cut out
It cuts, is adhered on base layer that obtain porous current collector stand-by using conductive rubber cement porous structure layer later, at this time obtained hole
Hole depth is 360 μm；
Remaining is same as Example 7, repeats no more.
Embodiment 9
Difference from Example 7 is, includes the following steps：
The preparation of porous current collector：Select the copper foil with a thickness of 100 μm as base layer；Select the copper with a thickness of 300 μm
Foil, later by the way of laser boring, chemical attack, carrying out punching to the copper foil to obtain hole shape is rectangular, hole etc.
Imitating diameter is 200 μm, the porous structure layer that pitch of holes (two bore edges) is 5 μm；Above-mentioned porous structure layer and collective layer are cut,
It is adhered on base layer that obtain porous current collector stand-by using conductive rubber cement porous structure layer later, obtained hole is deep at this time
Degree is 600 μm；
Remaining is same as Example 7, repeats no more.
Embodiment 10
Difference from Example 7 is, includes the following steps：
The preparation of porous current collector：Select the copper foil with a thickness of 100 μm as base layer；Select the copper with a thickness of 300 μm
Foil, later by the way of laser boring, chemical attack, carrying out punching to the copper foil to obtain hole shape is rectangular, hole etc.
Imitating diameter is 200 μm, the porous structure layer that pitch of holes (two bore edges) is 5 μm；Above-mentioned porous structure layer and collective layer are cut,
It is adhered on base layer that obtain porous current collector stand-by using conductive rubber cement porous structure layer later, obtained hole is deep at this time
Degree is 1200 μm；
Remaining is same as Example 7, repeats no more.
Embodiment 11
Difference from Example 7 is, includes the following steps：
Porous current collector base layer material is nickel；Porous structure layer material is that polypyrrole finally obtains with a thickness of 500 μm
Porous current collector hole depth be 750 μm, negative electrode active material is graphite.
Remaining is same as Example 7, repeats no more.
Embodiment 12
Difference from Example 7 is, includes the following steps：
Porous current collector base layer material is rustless steel；Porous structure layer material is polyaniline, negative electrode active material two
Aoxidize manganese material.
Remaining is same as Example 7, repeats no more.
Embodiment 13
Difference from Example 1 is that the present embodiment includes the following steps：
The preparation of porous current collector：Select the copper foil with a thickness of 1 μm as base layer；The copper foil with a thickness of 5 μm is selected, it
Afterwards by the way of laser boring, carrying out punching to the copper foil to obtain hole shape is circle, bore dia is 2 μm, pitch of holes
(two bore edges) are 1 μm, hole depth is 5 μm of hole, to obtain the porous structure layer of porous current collector；By above-mentioned porous knot
Structure layer and collective layer are cut, and are adhered on base layer that obtain porous current collector stand-by using conductive rubber cement porous structure layer later；
Remaining is same as Example 1, repeats no more.
Embodiment 14
Difference from Example 1 is that the present embodiment includes the following steps：
The preparation of porous current collector：Select the copper foil with a thickness of 1 μm as base layer；The copper foil with a thickness of 20 μm is selected,
Later by the way of laser boring, carrying out punching to the copper foil to obtain hole shape is circle, bore dia is 2 μm, Kong Jian
Away from (two bore edges) be 1 μm, hole depth is 20 μm of hole, to obtain the porous structure layer of porous current collector；It will be above-mentioned more
Pore structure layer and collective layer are cut, and are adhered on base layer using conductive rubber cement porous structure layer later and are obtained porous current collector and wait for
With；
Remaining is same as Example 1, repeats no more.
Embodiment 15
Difference from Example 1 is that the present embodiment includes the following steps：
The preparation of porous current collector：Select the copper foil with a thickness of 1 μm as base layer；The copper foil with a thickness of 50 μm is selected,
Later by the way of laser boring, carrying out punching to the copper foil to obtain hole shape is circle, bore dia is 2 μm, Kong Jian
Away from (two bore edges) be 1 μm, hole depth is 50 μm of hole, to obtain the porous structure layer of porous current collector；It will be above-mentioned more
Pore structure layer and collective layer are cut, and are adhered on base layer using conductive rubber cement porous structure layer later and are obtained porous current collector and wait for
With；
Remaining is same as Example 1, repeats no more.
Volume test：Volume test is carried out by battery core of the following process to comparative example and each embodiment in 35 DEG C of environment：
Stand 3min；0.5C constant-current charge is to 4.2V, constant-voltage charge to 0.05C；Stand 3min；0.5C constant-current discharge obtains head to 3.0V
Secondary discharge capacity D0；It stands 3min and completes volume test later；Acquired results are shown in Table 1.
Bending：Battery core flexible in comparative example and each embodiment is subjected to the bending of 0 degree~180 degree, is bent number 500 times；It
Volume test is carried out to comparative example and each embodiment according to the above process respectively afterwards.
Battery core high rate performance tests (taking battery core after volume test)：The lithium ion that comparative example and each embodiment are prepared
Battery carries out multiplying power test.Battery core is subjected to multiplying power test in 35 DEG C of environment, process is：Stand 3min；0.5C constant-current charge
To 4.2V, constant-voltage charge to 0.05C；Stand 3min；0.2C constant-current discharge obtains discharge capacity D0 for the first time to 3.0V.It stands
3min；0.5C constant-current charge is to 4.2V, constant-voltage charge to 0.05C；Stand 3min；2C constant-current discharge is discharged for the first time to 3.0V
Capacity D1.High rate performance Rate=D1/D0, acquired results are shown in Table 1.
The electrical property table of the energy storage device of table 1, comparative example and embodiment
By table 1, comparative examples 1, Examples 1 to 6 can be obtained, using flexible battery prepared by the present invention, after bending 500 times
Battery capacity conservation rate is higher, illustrates that battery of the invention has better comprehensive performance.
Flexible battery core prepared by embodiment 1,2 is placed in 60 DEG C, is stored 20 days in the environment of 95% humidity, finds embodiment
1 flexible battery core flatulence, the battery core of embodiment 2 is intact, this is because the not perforated thickness h of the porous current collector of embodiment 1 is too small
(1 μm) can not play the role of intact barrier aqueous vapor, therefore aqueous vapor is penetrated into inside battery core and led in hot and humid environment
It sends a telegraph core and produces gas.
4~embodiment of comparative example 6 is found, as the effective aperture of porous current collector becomes larger, is prepared
The high rate performance of flexible device is poorer, this is because collector can serve as electronic conductor when porous current collector hole is smaller,
The electric conductivity for increasing silicon electrode, to prepare the excellent flexible battery of high rate performance；But when effective aperture is larger, afflux
Electronics on body is difficult to conduct to being located at the silicon active material at hole center, therefore will affect the high rate performance of flexible device.And
And effective aperture it is smaller when, be also beneficial to constraint of the pore structure to volume expansion after the embedding lithium of silicon materials, it is absolute to reduce electrode expansion
Value is conducive to the structural stability for improving electrode, improves the cycle performance of flexible battery.
8~embodiment of comparative example 10 it can be found that with porous current collector hole length increase, what is prepared is soft
The high rate performance of property device gradually decreases, this is because being filled into pore structure with the increase of porous current collector hole length
Ion diffusion path of the silicon active material in charge and discharge process is longer, therefore the high rate performance of battery is poorer.
It can be obtained by each embodiment, the present invention has universality, collector, different negative electrode active materials to unlike material
Matter is suitable for the present invention.
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula is changed and is modified.Therefore, the invention is not limited to above-mentioned specific embodiment, all those skilled in the art exist
Made any conspicuous improvement, replacement or modification all belong to the scope of protection of the present invention on the basis of the present invention.This
Outside, although using some specific terms in this specification, these terms are merely for convenience of description, not to the present invention
Constitute any restrictions.
Claims (10)
1. a kind of flexible device, including a piece of positive plate, a piece of negative electrode tab and isolation film, the negative electrode tab is by negative electrode active material
It is formed with negative current collector, it is characterised in that：
The negative current collector is made of porous structure layer and base layer, and the porous structure layer is attached to the base layer table
Face；
The porous structure layer includes pore structure area and non-porose area, and the volume of the pore structure area and non-porose area is respectively V1, V2,
And V1/ (V1+V2) >=10%；
The negative electrode active material is distributed in the pore structure of the porous structure layer or the non-porose area of the porous structure layer
Surface, the quality for being distributed in the active material in the pore structure of the porous structure layer is W1, is distributed in the porous structure layer
The quality of active material on non-porose area surface be W2, and W1/ (W1+W2) >=10%；
The porous structure layer is conducting polymer.
2. a kind of flexible device described in claim 1, which is characterized in that the base layer is metal simple-substance, metal and metal
At least one of alloy, metal and non-metal alloy, or formed with other materials for metal simple-substance or its alloy compound
Material, and the base layer with a thickness of h, and h is greater than or equal to 1 μm.
3. a kind of flexible device described in claim 1, which is characterized in that the porous structure layer of the collector with a thickness of a,
And 5 μm≤a≤1000 μm；The hole equivalent diameter of the porous structure structure sheaf is d, and 0.1 μm≤d≤2cm；The porous knot
The pore wall thickness of structure layer is b, and 0.01 μm≤b≤1cm；The hole length of the porous structure layer is L, and L≤4a.
4. a kind of flexible device as claimed in claim 3, which is characterized in that 10 μm≤h≤100 μm, 20 μm≤a≤500 μm,
0.6 μm≤d≤1cm, 0.05 μm≤b≤10mm, L≤2a；The hole shape of the porous structure layer is round, oval, polygon
At least one of shape.
5. a kind of described in any item flexible devices of Claims 1 to 4, which is characterized in that V1/ (V1+V2) >=50%；W1/(W1
+ W2) >=50%.
6. a kind of flexible device described in claim 1, which is characterized in that also contain conductive agent in the negative electrode active material
Or/and bonding agent；The porous structure layer has conductive capability, and the hole in the pore structure area runs through the entire porous knot
Structure layer；Be provided with conductive adhesion layer between the porous structure layer and the base layer, and the conductive adhesion layer with a thickness of
C, c≤1 μm.
7. a kind of flexible device as claimed in claim 2, which is characterized in that the metal include Mg, Ca, Sr, Ba, Ra, Al,
Ga、In、Ge、Sn、Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Ru、Rh、Pd、Ag、Cd、La、W、Pt、
At least one of Au, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu；It is described it is nonmetallic include H, B, C, N,
O, at least one of Si, P, S, As, Se, Te, F, Cl, Br, I；The other materials is polymer composite, the macromolecule
Composite material includes polypyrrole (PPy), polyaniline (PANi), polyacrylonitrile (PAN), Polyglycolic acid fibre (PEDOT), polycyclic
At least one of oxidative ethane (PEO) and polyethylene glycol (PEG).
8. a kind of flexible device described in claim 1, which is characterized in that the conducting polymer includes polythiophene and its derivative
At least one of object, polypyrrole and its derivative, Polyaniline and its derivative, polyacetylene, conducting resinl.
9. a kind of preparation method of flexible device described in claim 1, which is characterized in that mainly include the following steps：
Step 1, prepared by porous current collector：Porous structure layer is prepared, substrate surface is arranged in, so that porous structure layer is attached to base
Material surface and electronic conduction, obtain porous current collector；
Step 2, prepared by negative electrode tab：Negative electrode active material is arranged in the porous structure layer side of porous current collector described in step 1,
Obtain negative electrode tab；
Step 3, flexible device assembles：Above-mentioned negative electrode tab and isolation film, positive plate are assembled, chemical conversion, shaping obtain flexible device.
10. a kind of preparation method of flexible device as claimed in claim 9, which is characterized in that porous structure layer described in step 1
Porous structure layer is prepared for porous structure layer or pore-free material is directly prepared by etching；The etching includes swashing
At least one of light ablation, chemical etching, quantum bombardment.
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| CN111048787A (en) * | 2019-12-11 | 2020-04-21 | 合肥国轩高科动力能源有限公司 | Manufacturing method of flexible composite current collector |
| CN111063860A (en) * | 2019-12-19 | 2020-04-24 | 深圳市倍特力电池有限公司 | Electrode plate, preparation method thereof and battery |
| CN111342053A (en) * | 2020-03-02 | 2020-06-26 | 太仓中科赛诺新能源科技有限公司 | Flexible integrated electrode plate and preparation method and application thereof |
| CN114081499B (en) * | 2021-11-23 | 2024-01-12 | 吉林大学 | Flexible transparent surface myoelectric electrode with two gradient holes and preparation method thereof |
| WO2023142430A1 (en) * | 2022-01-28 | 2023-08-03 | 厦门海辰储能科技股份有限公司 | Composite current collector, method for preparing composite current collector, electrode plate, battery, and electric device |
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