CN108878886A - A kind of battery thickness pole piece and its water base compound binding agent - Google Patents
A kind of battery thickness pole piece and its water base compound binding agent Download PDFInfo
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- CN108878886A CN108878886A CN201810752383.6A CN201810752383A CN108878886A CN 108878886 A CN108878886 A CN 108878886A CN 201810752383 A CN201810752383 A CN 201810752383A CN 108878886 A CN108878886 A CN 108878886A
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- pole piece
- polymer
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
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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
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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
Abstract
The invention belongs to battery technology field more particularly to a kind of water base compound binding agents of battery thickness pole piece, by weight, include at least following component：Fluoroethylene polymer 5-8 parts by weight；It is crosslinked water absorbent polymer 0.5-1 parts by weight；Water 20-40 parts by weight；Fluoroethylene polymer and crosslinking water absorbent polymer formation intertwine with each other staggered polymer network.Compared with the existing technology, in the present invention, the strand for being crosslinked water absorbent polymer is reticular structure, fluoroethylene polymer and crosslinking water absorbent polymer interaction make macromolecular chain and macromolecule reticular structure interact, formation intertwine with each other staggered polymer network, the phenomenon that binder dissolution will not occurs placing for a long time in the electrolytic solution.
Description
Technical field
The invention belongs to battery technology field more particularly to a kind of battery thickness pole pieces and its water base compound binding agent.
Background technique
Lithium ion battery has the characteristics that energy density is high, operating voltage is high, self discharge is small, but due to using Organic Electricity
Liquid is solved, the solvent selection organic solvent (generally N-Methyl pyrrolidone (NMP)) of electrolyte is volatile, inflammable and explosive, right
Human body and environment suffer from serious harm and pollution, and there are security risks.And water base battery compared to organic system have low cost,
The advantage of high security.This is because water base battery uses common, environmentally friendly and inexpensive water as solvent.
SBR or PTFE is mostly used in binder in water base battery.But the cohesive force of SBR is weaker, leads to battery-active
Material bonds loosely, and then causes the cyclical stability of battery poor, influences battery life.PTFE emulsion and PVDF solution can be made
For water-based binder, although cohesive force is pretty good, since PTFE emulsion has water solubility, with soaking time in the electrolytic solution
Increase and charge and discharge cycles progress, PTFE has dissolution problem, to cause pole piece soften, drop off, capacity decline, into
And cause circulating battery stability bad.
On the other hand, the battery pole piece for being added to PTFE and PVDF has lower surface energy, so that pole piece be caused to infiltrate
The bad problem of property, increases the internal resistance of pole piece and reduces battery pole piece intermediate ion transmission speed, in turn result in battery capacity
The appearance for the problems such as performance is bad and polarization increases.
In addition, the preparation process of water base cell size is largely slurry technique at present, feature is that pole piece thickness is thin, is led
Electrically excellent, high rate performance is excellent, but it needs to use a large amount of collector as support, causes certain waste of material,
And pole piece is bulky, it is difficult to realize thick electrode.
In view of this, the present invention is intended to provide a kind of water base compound binding agent of battery thickness pole piece, has inexpensive, green
The advantages that colour circle is protected, preparation method is simple prepares water system battery thickness pole piece with the binder, can reduce the polarization of pole piece, increase
Add the mechanical stability of pole piece, and solve the problems, such as binder dissolution, to improve the battery using the thickness pole piece
Cyclical stability.
Summary of the invention
It is an object of the present invention to：In view of the deficiencies of the prior art, a kind of battery thickness pole piece is provided with water base multiple
Binder is closed, has many advantages, such as that inexpensive, environmentally protective, preparation method is simple, prepares water system battery thickness pole with the binder
Piece can reduce the polarization of pole piece, increase the mechanical stability of pole piece, and solve the problems, such as binder dissolution, to mention
The cyclical stability of the high battery using the thickness pole piece.
In order to achieve the above object, the present invention adopts the following technical scheme that：
A kind of water base compound binding agent of battery thickness pole piece includes at least following component by weight：
Fluoroethylene polymer 5-8 parts by weight；
It is crosslinked water absorbent polymer 0.5-1 parts by weight；
Water 20-40 parts by weight；
The fluoroethylene polymer and crosslinking water absorbent polymer formation intertwine with each other staggered polymer network.
Fluoroethylene polymer, the weight ratio for being crosslinked water absorbent polymer must within the above range, and the pole piece of preparation could not
Picking does not dissolve, does not have the phenomenon that binder dissolution in placement process, charge-discharge performance is excellent.More than this numerical value
When range, there is phenomena such as polarization is big, and cyclical stability is bad in pole piece.
As a kind of improvement of the water base compound binding agent of battery thickness pole piece of the present invention, the fluoroethylene polymer is PTFE
And/or PVDF.PTFE emulsion and PVDF lotion are macromolecular chain shaped polymer, and bonding mechanism is and powder (conductive agent, activity
Substance) be sufficiently mixed after, macromolecular chain will form network-like structure and intertwine with each other so that the mutual tied up in knots of powder,
Reach bond effect, if PTFE emulsion and PVDF solution can make thick pole piece not lose powder merely from physical mechanical property,
Surface is smooth.But because thick pole piece is to apply to carry out charge and discharge in aqueous electrolyte, and PTFE and PVDF is because its is low
Surface energy, so not high using the pole piece water retention that it is prepared, the wellability of water is poor, and pole is caused in battery charge and discharge process
The problems such as change is big, and capacity performance is undesirable, and stable circulation is bad.
As a kind of improvement of the water base compound binding agent of battery thickness pole piece of the present invention, the crosslinking water absorbent polymer is to hand over
Join at least one of sodium carboxymethylcellulose, crosslinking sodium polyacrylate, crosslinked polyvinylpyrrolidone.The present invention is using crosslinking
Water absorbent polymer (croscarmellose sodium, crosslinking sodium polyacrylate, crosslinked polyvinylpyrrolidone) and vinyl fluoride polymerization
Object is used collectively as the binder of water base thick pole piece.On the one hand, crosslinking water absorbent polymer due in its molecular structure containing compared with
Have hydrophilic functional group, therefore have strong hydrophily and water-retaining property, can increase thick pole piece water absorption rate and
Water retention reduces the polarization generated in charge and discharge process, and improves pole piece capacity and play bad problem, improves pole piece
Cyclical stability.On the other hand, crosslinking water absorbent polymer is macromolecule reticular structure, can be by fluorine by being fully ground mixing
The macromolecule reticular structure of polyvinyl macromolecule chain and crosslinking water absorbent polymer carries out entanglement mixing, and interact shape
At the network structure of binder, the interaction between binder had both been increased, thick pole piece is prevented to be placed on aqueous electrolyte for a long time
In binder dissolve out problem, also increase and effect be firmly bonded to active material and conductive agent dry powder.
As a kind of improvement of the water base compound binding agent of battery thickness pole piece of the present invention, the fluoroethylene polymer is averaged
Molecular weight is 600,000-80 ten thousand.
As a kind of improvement of the water base compound binding agent of battery thickness pole piece of the present invention, the croscarmellose sodium
Average molecular weight be 600,000-80 ten thousand, the molecular weight of crosslinking sodium polyacrylate is 3,000,000-700 ten thousand, crosslinked polyethylene pyrrolidines
The average molecular weight of ketone is 40,000-8 ten thousand.The selection of the above molecular weight is based on viscosity and adhesive property satisfaction within this range
Product demand, and show excellent performance.
As a kind of improvement of the water base compound binding agent of battery thickness pole piece of the present invention, the friendship of the crosslinking water absorbent polymer
Connection degree is 60%-85%, is crosslinked in range herein, and crosslinking water absorbent polymer had both had certain swellbility or had certain bonding
Property.
Compared with the existing technology, in the present invention, the strand for being crosslinked water absorbent polymer is reticular structure, fluoroethylene polymer
Macromolecular chain and macromolecule reticular structure is set to interact with crosslinking water absorbent polymer interaction, formation intertwine with each other staggered
Polymer network the phenomenon that binder dissolution will not occur placing for a long time in the electrolytic solution.And it is found through experiments that
The bonding that fluoroethylene polymer and uncrosslinked water absorbent polymer (sodium carboxymethylcellulose, polyvinylpyrrolidone) are mixed to get
The phenomenon that having binder dissolution, is placed in agent for a long time in the electrolytic solution, this may be because two macromolecular chains are intertwine with each other
Force ratio it is weaker, and fluoroethylene polymer and uncrosslinked water absorbent polymer both binders in water dispersibility compared with
It is good, it places have binder dissolution for a long time.
The present invention also provides a kind of battery thickness pole pieces, the active matter including collector and coated on the collection liquid surface
Matter layer, the active material layer include active material, bonding agent and conductive agent, and the bonding agent is bonding of the present invention
Agent.Pole piece includes positive plate and negative electrode tab, and positive active material includes cobalt acid lithium, LiMn2O4, lithium nickelate, nickle cobalt lithium manganate, nickel
Cobalt lithium aluminate, ferronickel are at least one of Prussian blue, and negative electrode active material includes hard carbon, soft carbon, natural graphite, artificial stone
At least one of ink, carbonaceous mesophase spherules, silicon-carbon compound etc..Conductive agent is superconduction carbon, graphene, carbon fiber, carbon nanometer
At least one of pipe.Plus plate current-collecting body is aluminium foil, and negative current collector is copper foil.Diaphragm using water system diaphragm (glass fibre every
Film, nonwoven wood diaphragm).The packaged type of battery is winding or lamination.
As a kind of improvement of battery thickness pole piece of the present invention, the preparation method of the pole piece includes the following steps：
Crosslinking water absorbent polymer is added to the water, is sufficiently stirred by the first step, forms crosslinking water absorbent polymer solution；Again will
Conductive agent and crosslinking water absorbent polymer solution are placed in mortar and are fully ground, and form conductive agent and crosslinking water absorbent polymer uniformly
Conductive network, active material is then added, is fully ground so that active material, conductive agent and crosslinking water absorbent polymer formed
Uniform conductive network and coherent network, obtain mixture；
Fluoroethylene polymer is added to the water by second step, is sufficiently stirred, and forms fluoroethylene polymer lotion；
The fluoroethylene polymer lotion of second step is added into the mixture that the first step obtains, is sufficiently stirred, obtains for third step
To half dry powder；
Half dry powder of third step is transferred on collector, tabletting by the 4th step, dry, obtains pole piece.
(croscarmellose sodium, crosslinking are poly- with crosslinking water absorbent polymer by common fluoroethylene polymer by the present invention
Sodium acrylate, crosslinked polyvinylpyrrolidone) it is compounded, pole piece is prepared by semidry method using the binder, less
Also it is able to maintain excellent bonding situation under solvent, does not crack, does not lose powder, it is steady that certain machinery is also able to maintain in aqueous electrolyte
It is qualitative, do not soften.(water suction polymerization is crosslinked by macromolecular chain shaped polymer (PTFE and PVDF) and macromolecule network polymers
Object) two binders are used in mixed way, and can form crosslinking polymer network, and intertwineing with each other between binder is increased, is avoided
The binder dissolution and pole piece softening situation that water-soluble binder occurs in the electrolytic solution for a long time.And it is thick using this positive and negative anodes
The water system full battery of pole piece preparation, has excellent volumetric properties and cyclical stability.In addition, the present invention is using a kind of novel
Semidry method prepares water system battery sheet, can increase the effective active matter quality in battery unit mass, reduce collector
It uses and wastes.
As a kind of improvement of battery thickness pole piece of the present invention, the active material layer with a thickness of 1mm-2mm.
As a kind of improvement of battery thickness pole piece of the present invention, active material, conductive agent, fluoroethylene polymer and crosslinking water suction
The weight ratio of polymer is (75~85):(9.5~16):(5~8):(0.5~1).
Compared with the existing technology, pole piece of the invention is smooth, does not lose powder, even if immersing in electrolyte 3 months, does not also have
There is the phenomenon that binder dissolution and sliver.Being used to assemble water system battery for thick pole piece prepared by semidry method of the invention has
Excellent capacity and cyclical stability, and pole piece still has excellent mechanical stability after circulation.And this method also has
Have the characteristics that inexpensive, environmentally protective, simple and easy
Specific embodiment
Below the technical scheme of the invention is illustrated by a specific example, but the scope of the present invention is not limited thereto.
Embodiment 1
A kind of water base compound binding agent of battery thickness pole piece is present embodiments provided, by weight, is included at least as follows
Component：
6 parts by weight of fluoroethylene polymer；
It is crosslinked 0.6 parts by weight of water absorbent polymer；
30 parts by weight of water；
Fluoroethylene polymer and crosslinking water absorbent polymer formation intertwine with each other staggered polymer network.
Fluoroethylene polymer is PTFE, and crosslinking water absorbent polymer is croscarmellose sodium, the mean molecule of PTFE
Amount is 700,000, and the average molecular weight of croscarmellose sodium is 700,000, and the degree of cross linking of croscarmellose sodium is
75%.
Embodiment 2
A kind of water base compound binding agent of battery thickness pole piece is present embodiments provided, by weight, is included at least as follows
Component：
7 parts by weight of fluoroethylene polymer；
It is crosslinked 0.9 parts by weight of water absorbent polymer；
35 parts by weight of water；
The fluoroethylene polymer and crosslinking water absorbent polymer formation intertwine with each other staggered polymer network.
The fluoroethylene polymer is PVDF.The crosslinking water absorbent polymer is crosslinking sodium polyacrylate.
The average molecular weight of the PVDF is 650,000.The molecular weight of crosslinking sodium polyacrylate is 4,000,000, cross linked polyacrylate
The degree of cross linking of sodium is 80%.
Embodiment 3
A kind of water base compound binding agent of battery thickness pole piece is present embodiments provided, by weight, is included at least as follows
Component：
6.5 parts by weight of fluoroethylene polymer；
It is crosslinked 0.75 parts by weight of water absorbent polymer；
28 parts by weight of water；
The fluoroethylene polymer and crosslinking water absorbent polymer formation intertwine with each other staggered polymer network.
Fluoroethylene polymer is PVDF.Crosslinking water absorbent polymer is crosslinked polyvinylpyrrolidone.Fluoroethylene polymer
The average molecular weight of PVDF is 680,000.The average molecular weight of crosslinked polyvinylpyrrolidone is 70,000.Crosslinked polyvinylpyrrolidone
The degree of cross linking be 65%.
Embodiment 4
A kind of water base compound binding agent of battery thickness pole piece is present embodiments provided, by weight, is included at least as follows
Component：
7.5 parts by weight of fluoroethylene polymer；
It is crosslinked 0.85 parts by weight of water absorbent polymer；
33 parts by weight of water；
The fluoroethylene polymer and crosslinking water absorbent polymer formation intertwine with each other staggered polymer network.
Fluoroethylene polymer is PTFE, and crosslinking water absorbent polymer is croscarmellose sodium and crosslinking sodium polyacrylate
Mixture, the mass ratio of the two is 1：1.The average molecular weight of fluoroethylene polymer is 730,000.Croscarmellose sodium
Average molecular weight be 630,000, the molecular weight of crosslinking sodium polyacrylate is 6,000,000.The degree of cross linking of croscarmellose sodium is
69%, the degree of cross linking of crosslinking sodium polyacrylate is 62%.
Embodiment 5
A kind of water base compound binding agent of battery thickness pole piece is present embodiments provided, by weight, is included at least as follows
Component：
5.5 parts by weight of fluoroethylene polymer；
It is crosslinked 0.62 parts by weight of water absorbent polymer；
27 parts by weight of water；
The fluoroethylene polymer and crosslinking water absorbent polymer formation intertwine with each other staggered polymer network.
Fluoroethylene polymer is PTFE.The crosslinking water absorbent polymer is crosslinking sodium polyacrylate and crosslinked polyethylene pyrroles
Alkanone, the mass ratio of the two are 1：2.The average molecular weight of PTFE is 780,000.The molecular weight of crosslinking sodium polyacrylate is 5,000,000,
The average molecular weight of crosslinked polyvinylpyrrolidone is 6.5 ten thousand.The degree of cross linking of crosslinking sodium polyacrylate is 82%, crosslinked polyethylene
The degree of cross linking of pyrrolidones is 74%.
Comparative example 1
This comparative example provides a kind of water base compound binding agent of battery thickness pole piece, by weight, includes at least as follows
Component：
6 parts by weight of fluoroethylene polymer；
0.6 parts by weight of water absorbent polymer；
30 parts by weight of water；
Fluoroethylene polymer is PTFE, and water absorbent polymer is sodium carboxymethylcellulose, and the average molecular weight of PTFE is 700,000.
Comparative example 2
This comparative example provides a kind of water base compound binding agent of battery thickness pole piece, by weight, includes at least as follows
Component：
7 parts by weight of fluoroethylene polymer；
0.9 parts by weight of water absorbent polymer；
35 parts by weight of water；
Fluoroethylene polymer is PVDF.Water absorbent polymer is Sodium Polyacrylate.The average molecular weight of PVDF is 650,000.
Comparative example 3
This comparative example provides a kind of water base compound binding agent of battery thickness pole piece, by weight, includes at least as follows
Component：
6.5 parts by weight of fluoroethylene polymer；
0.75 parts by weight of water absorbent polymer；
28 parts by weight of water；
Fluoroethylene polymer is PVDF.Water absorbent polymer is polyvinylpyrrolidone.Fluoroethylene polymer PVDF's is averaged
Molecular weight is 680,000.
Comparative example 4
This comparative example provides a kind of water base compound binding agent of battery thickness pole piece, by weight, includes at least as follows
Component：
6 parts by weight of fluoroethylene polymer；
30 parts by weight of water；
Fluoroethylene polymer is PTFE, and the average molecular weight of PTFE is 700,000.
Comparative example 5
This comparative example provides a kind of water base compound binding agent of battery thickness pole piece, by weight, includes at least as follows
Component：
It is crosslinked 0.62 parts by weight of water absorbent polymer；
27 parts by weight of water；
Crosslinking water absorbent polymer is crosslinking sodium polyacrylate.The molecular weight of crosslinking sodium polyacrylate is 5,000,000.
Embodiment 6
A kind of battery thickness positive plate is present embodiments provided, including plus plate current-collecting body and coated on plus plate current-collecting body surface
Positive electrode active material layer, positive electrode active material layer include positive active material cobalt acid lithium, bonding agent and conductive agent superconduction carbon, bonding
Agent is bonding agent described in embodiment 1.
The preparation method of the pole piece includes the following steps：
Crosslinking water absorbent polymer is added to the water, is sufficiently stirred by the first step, forms crosslinking water absorbent polymer solution；Again will
Conductive agent and crosslinking water absorbent polymer solution are placed in mortar and are fully ground, and form conductive agent and crosslinking water absorbent polymer uniformly
Conductive network, then be added positive active material cobalt acid lithium, be fully ground, so that positive active material, conductive agent and crosslinking
Water absorbent polymer forms uniform conductive network and coherent network, obtains mixture；
Fluoroethylene polymer is added to the water by second step, is sufficiently stirred, and forms fluoroethylene polymer lotion；
The fluoroethylene polymer lotion of second step is added into the mixture that the first step obtains, is sufficiently stirred, obtains for third step
To half dry powder；
Half dry powder of third step is transferred on plus plate current-collecting body aluminium foil, tabletting by the 4th step, dry, obtains pole piece.The pole
Positive electrode active material layer with a thickness of 1.5mm in piece, wherein positive active material, conductive agent, fluoroethylene polymer and crosslinking are inhaled
The weight ratio of aqueous polymer is 81:12.4:6:0.6.
Embodiment 7
A kind of battery thickness positive plate is present embodiments provided, including plus plate current-collecting body and coated on plus plate current-collecting body surface
Positive electrode active material layer, positive electrode active material layer include positive active material lithium nickelate, bonding agent and conductive agent carbon fiber, bonding
Agent is bonding agent as described in example 2.
The preparation method of the pole piece includes the following steps：
Crosslinking water absorbent polymer is added to the water, is sufficiently stirred by the first step, forms crosslinking water absorbent polymer solution；Again will
Conductive agent and crosslinking water absorbent polymer solution are placed in mortar and are fully ground, and form conductive agent and crosslinking water absorbent polymer uniformly
Conductive network, then be added positive active material lithium nickelate, be fully ground, so that positive active material, conductive agent and crosslinking
Water absorbent polymer forms uniform conductive network and coherent network, obtains mixture；
Fluoroethylene polymer is added to the water by second step, is sufficiently stirred, and forms fluoroethylene polymer lotion；
The fluoroethylene polymer lotion of second step is added into the mixture that the first step obtains, is sufficiently stirred, obtains for third step
To half dry powder；
Half dry powder of third step is transferred on plus plate current-collecting body aluminium foil, tabletting by the 4th step, dry, obtains pole piece.The pole
Positive electrode active material layer with a thickness of 1.3mm in piece, wherein positive active material, conductive agent, fluoroethylene polymer and crosslinking are inhaled
The weight ratio of aqueous polymer is 79:13.1:7:0.9.
Embodiment 8
A kind of battery thickness positive plate is present embodiments provided, including plus plate current-collecting body and coated on plus plate current-collecting body surface
Positive electrode active material layer, positive electrode active material layer include positive active material LiMn2O4, bonding agent and conductive agent graphene, bonding
Agent is bonding agent described in embodiment 3.
The preparation method of the pole piece includes the following steps：
Crosslinking water absorbent polymer is added to the water, is sufficiently stirred by the first step, forms crosslinking water absorbent polymer solution；Again will
Conductive agent and crosslinking water absorbent polymer solution are placed in mortar and are fully ground, and form conductive agent and crosslinking water absorbent polymer uniformly
Conductive network, then be added positive active material LiMn2O4, be fully ground, so that positive active material, conductive agent and crosslinking
Water absorbent polymer forms uniform conductive network and coherent network, obtains mixture；
Fluoroethylene polymer is added to the water by second step, is sufficiently stirred, and forms fluoroethylene polymer lotion；
The fluoroethylene polymer lotion of second step is added into the mixture that the first step obtains, is sufficiently stirred, obtains for third step
To half dry powder；
Half dry powder of third step is transferred on plus plate current-collecting body aluminium foil, tabletting by the 4th step, dry, obtains pole piece.The pole
Positive electrode active material layer with a thickness of 1.8mm in piece, wherein positive active material, conductive agent, fluoroethylene polymer and crosslinking are inhaled
The weight ratio of aqueous polymer is 82:10.75:6.5:0.75.
Embodiment 9
A kind of battery thickness positive plate is present embodiments provided, including plus plate current-collecting body and coated on plus plate current-collecting body surface
Positive electrode active material layer, positive electrode active material layer include positive active material nickle cobalt lithium manganate, bonding agent and conductive agent carbon nanometer
Pipe, bonding agent are bonding agent as described in example 4.
The preparation method of the pole piece includes the following steps：
Crosslinking water absorbent polymer is added to the water, is sufficiently stirred by the first step, forms crosslinking water absorbent polymer solution；Again will
Conductive agent and crosslinking water absorbent polymer solution are placed in mortar and are fully ground, and form conductive agent and crosslinking water absorbent polymer uniformly
Conductive network, then be added positive active material nickle cobalt lithium manganate, be fully ground so that positive active material, conductive agent and
Crosslinking water absorbent polymer forms uniform conductive network and coherent network, obtains mixture；
Fluoroethylene polymer is added to the water by second step, is sufficiently stirred, and forms fluoroethylene polymer lotion；
The fluoroethylene polymer lotion of second step is added into the mixture that the first step obtains, is sufficiently stirred, obtains for third step
To half dry powder；
Half dry powder of third step is transferred on plus plate current-collecting body aluminium foil, tabletting by the 4th step, dry, obtains pole piece.The pole
Positive electrode active material layer with a thickness of 1.1mm in piece, wherein positive active material, conductive agent, fluoroethylene polymer and crosslinking are inhaled
The weight ratio of aqueous polymer is 77:14.65:7.5:0.85.
Embodiment 10
A kind of battery thickness positive plate is present embodiments provided, including plus plate current-collecting body and coated on plus plate current-collecting body surface
Positive electrode active material layer, positive electrode active material layer include positive active material nickel cobalt lithium aluminate, bonding agent and conductive agent carbon nanometer
Pipe, bonding agent are bonding agent described in embodiment 5.
The preparation method of the pole piece includes the following steps：
Crosslinking water absorbent polymer is added to the water, is sufficiently stirred by the first step, forms crosslinking water absorbent polymer solution；Again will
Conductive agent and crosslinking water absorbent polymer solution are placed in mortar and are fully ground, and form conductive agent and crosslinking water absorbent polymer uniformly
Conductive network, then be added positive active material nickel cobalt lithium aluminate, be fully ground so that positive active material, conductive agent and
Crosslinking water absorbent polymer forms uniform conductive network and coherent network, obtains mixture；
Fluoroethylene polymer is added to the water by second step, is sufficiently stirred, and forms fluoroethylene polymer lotion；
The fluoroethylene polymer lotion of second step is added into the mixture that the first step obtains, is sufficiently stirred, obtains for third step
To half dry powder；
Half dry powder of third step is transferred on plus plate current-collecting body aluminium foil, tabletting by the 4th step, dry, obtains pole piece.The pole
Positive electrode active material layer with a thickness of 1.1mm in piece, wherein positive active material, conductive agent, fluoroethylene polymer and crosslinking are inhaled
The weight ratio of aqueous polymer is 82.5:11.38:5.5:0.62.
Embodiment 11
A kind of battery thickness negative electrode tab is present embodiments provided, including negative current collector and coated on negative current collector surface
Negative electrode active material layer, negative electrode active material layer include negative electrode active material silicon-carbon cathode, bonding agent and conductive agent superconduction carbon, are glued
Connecing agent is bonding agent described in embodiment 1.
The preparation method of the pole piece includes the following steps：
Crosslinking water absorbent polymer is added to the water, is sufficiently stirred by the first step, forms crosslinking water absorbent polymer solution；Again will
Conductive agent and crosslinking water absorbent polymer solution are placed in mortar and are fully ground, and form conductive agent and crosslinking water absorbent polymer uniformly
Conductive network, then be added negative electrode active material silicon-carbon cathode, be fully ground, so that negative electrode active material, conductive agent and friendship
Connection water absorbent polymer forms uniform conductive network and coherent network, obtains mixture；
Fluoroethylene polymer is added to the water by second step, is sufficiently stirred, and forms fluoroethylene polymer lotion；
The fluoroethylene polymer lotion of second step is added into the mixture that the first step obtains, is sufficiently stirred, obtains for third step
To half dry powder；
Half dry powder of third step is transferred on negative current collector copper foil, tabletting by the 4th step, dry, obtains pole piece.The pole
Negative electrode active material layer with a thickness of 1.6mm in piece, wherein negative electrode active material, conductive agent, fluoroethylene polymer and crosslinking are inhaled
The weight ratio of aqueous polymer is 81:12.4:6:0.6.
Embodiment 12
A kind of battery thickness negative electrode tab is present embodiments provided, including negative current collector and coated on negative current collector surface
Negative electrode active material layer, negative electrode active material layer include negative electrode active material carbonaceous mesophase spherules, bonding agent and conductive agent carbon fiber
Dimension, bonding agent are bonding agent as described in example 2.
The preparation method of the pole piece includes the following steps：
Crosslinking water absorbent polymer is added to the water, is sufficiently stirred by the first step, forms crosslinking water absorbent polymer solution；Again will
Conductive agent and crosslinking water absorbent polymer solution are placed in mortar and are fully ground, and form conductive agent and crosslinking water absorbent polymer uniformly
Conductive network, then be added negative electrode active material carbonaceous mesophase spherules, be fully ground, so that negative electrode active material, conductive agent
And crosslinking water absorbent polymer forms uniform conductive network and coherent network, obtains mixture；
Fluoroethylene polymer is added to the water by second step, is sufficiently stirred, and forms fluoroethylene polymer lotion；
The fluoroethylene polymer lotion of second step is added into the mixture that the first step obtains, is sufficiently stirred, obtains for third step
To half dry powder；
Half dry powder of third step is transferred on negative current collector copper foil, tabletting by the 4th step, dry, obtains pole piece.The pole
Negative electrode active material layer with a thickness of 1.55mm in piece, wherein negative electrode active material, conductive agent, fluoroethylene polymer and crosslinking
The weight ratio of water absorbent polymer is 79:13.1:7:0.9.
Embodiment 13
A kind of battery thickness negative electrode tab is present embodiments provided, including negative current collector and coated on negative current collector surface
Negative electrode active material layer, negative electrode active material layer include negative electrode active material hard carbon, bonding agent and conductive agent graphene, bonding agent
For bonding agent described in embodiment 3.
The preparation method of the pole piece includes the following steps：
Crosslinking water absorbent polymer is added to the water, is sufficiently stirred by the first step, forms crosslinking water absorbent polymer solution；Again will
Conductive agent and crosslinking water absorbent polymer solution are placed in mortar and are fully ground, and form conductive agent and crosslinking water absorbent polymer uniformly
Conductive network, then be added negative electrode active material hard carbon, be fully ground so that negative electrode active material, conductive agent and crosslinking inhale
Aqueous polymer forms uniform conductive network and coherent network, obtains mixture；
Fluoroethylene polymer is added to the water by second step, is sufficiently stirred, and forms fluoroethylene polymer lotion；
The fluoroethylene polymer lotion of second step is added into the mixture that the first step obtains, is sufficiently stirred, obtains for third step
To half dry powder；
Half dry powder of third step is transferred on negative current collector copper foil, tabletting by the 4th step, dry, obtains pole piece.The pole
Negative electrode active material layer with a thickness of 1.25mm in piece, wherein negative electrode active material, conductive agent, fluoroethylene polymer and crosslinking
The weight ratio of water absorbent polymer is 82:10.75:6.5:0.75.
Embodiment 14
A kind of battery thickness negative electrode tab is present embodiments provided, including negative current collector and coated on negative current collector surface
Negative electrode active material layer, negative electrode active material layer include negative electrode active material natural graphite, bonding agent and conductive agent superconduction carbon, are glued
Connecing agent is bonding agent as described in example 4.
The preparation method of the pole piece includes the following steps：
Crosslinking water absorbent polymer is added to the water, is sufficiently stirred by the first step, forms crosslinking water absorbent polymer solution；Again will
Conductive agent and crosslinking water absorbent polymer solution are placed in mortar and are fully ground, and form conductive agent and crosslinking water absorbent polymer uniformly
Conductive network, then be added negative electrode active material natural graphite, be fully ground, so that negative electrode active material, conductive agent and friendship
Connection water absorbent polymer forms uniform conductive network and coherent network, obtains mixture；
Fluoroethylene polymer is added to the water by second step, is sufficiently stirred, and forms fluoroethylene polymer lotion；
The fluoroethylene polymer lotion of second step is added into the mixture that the first step obtains, is sufficiently stirred, obtains for third step
To half dry powder；
Half dry powder of third step is transferred on negative current collector copper foil, tabletting by the 4th step, dry, obtains pole piece.The pole
Positive electrode active material layer with a thickness of 1.2mm in piece, wherein negative electrode active material, conductive agent, fluoroethylene polymer and crosslinking are inhaled
The weight ratio of aqueous polymer is 77:14.65:7.5:0.85.
Embodiment 15
A kind of battery thickness negative electrode tab is present embodiments provided, including negative current collector and coated on negative current collector surface
Negative electrode active material layer, negative electrode active material layer include negative electrode active material artificial graphite, bonding agent and conductive agent graphene, are glued
Connecing agent is bonding agent described in embodiment 5.
The preparation method of the pole piece includes the following steps：
Crosslinking water absorbent polymer is added to the water, is sufficiently stirred by the first step, forms crosslinking water absorbent polymer solution；Again will
Conductive agent and crosslinking water absorbent polymer solution are placed in mortar and are fully ground, and form conductive agent and crosslinking water absorbent polymer uniformly
Conductive network, then be added negative electrode active material artificial graphite, be fully ground, so that negative electrode active material, conductive agent and friendship
Connection water absorbent polymer forms uniform conductive network and coherent network, obtains mixture；
Fluoroethylene polymer is added to the water by second step, is sufficiently stirred, and forms fluoroethylene polymer lotion；
The fluoroethylene polymer lotion of second step is added into the mixture that the first step obtains, is sufficiently stirred, obtains for third step
To half dry powder；
Half dry powder of third step is transferred on negative current collector copper foil, tabletting by the 4th step, dry, obtains pole piece.The pole
Positive electrode active material layer with a thickness of 1.4mm in piece, wherein negative electrode active material, conductive agent, fluoroethylene polymer and crosslinking are inhaled
The weight ratio of aqueous polymer is 82.5:11.38:5.5:0.62.
Comparative example 6
This comparative example provides a kind of battery thickness positive plate, including plus plate current-collecting body and coated on plus plate current-collecting body surface
Positive electrode active material layer, positive electrode active material layer include positive active material cobalt acid lithium, bonding agent and conductive agent superconduction carbon, bonding
Agent is bonding agent described in comparative example 1.Positive electrode active material layer with a thickness of 1.5mm in the pole piece, wherein positive electrode active material
Matter, conductive agent, bonding agent weight ratio be 81:12.4:6.6.
Comparative example 7-10
Unlike comparative example 6, bonding agent is the bonding agent of comparative example 2-5, remaining is the same as comparative example 6.
Comparative example 11
This comparative example provides a kind of battery thickness negative electrode tab, including negative current collector and coated on negative current collector surface
Negative electrode active material layer, negative electrode active material layer include negative electrode active material silicon-carbon cathode, bonding agent and conductive agent superconduction carbon, are glued
Connecing agent is bonding agent described in comparative example 1.Negative electrode active material layer with a thickness of 1.6mm in the pole piece, wherein negative electrode active material
Matter, conductive agent, bonding agent weight ratio be 81:12.4:6.6.
Comparative example 12-15
Unlike comparative example 11, bonding agent is the bonding agent of comparative example 2-5, remaining is the same as comparative example 11.
Stability test in aqueous electrolyte is carried out to the pole piece that embodiment 6-15 and comparative example 6-15 is provided：At room temperature
Embodiment 6-15 and comparative example the 6-15 pole piece provided are placed in 3 months observation phenomenons in electrolyte by (25 DEG C), if dissolution,
Whether lose powder, if softening, if having phenomena such as binder dissolution, the results are shown in Table 1.
Table 1：The physical property for the pole piece that embodiment 6-15 and comparative example 6-15 is provided
As can be seen from Table 1, pole piece of the invention mechanical strength with higher, and do not lose powder, surface is smooth, by it
It is placed in aqueous electrolyte 3 months, also still keeps good mechanical performance, it is undissolved, phenomenon is dissolved out without binder.
Capacity retention ratio test：At room temperature, the negative electrode tab of the positive plate of embodiment 6-10 and embodiment 11-15 are assembled
Battery is obtained, number S1-S5 assembles the negative electrode tab of the positive plate of comparative example 6-10 and comparative example 11-15 to obtain battery, compiles
Number be D1-D5, upper limit blanking voltage is charged to the electric current of 0.1C, then carries out shelving 10min, then with same 0.1C into
Row is discharged to low cutoff voltage.Capacity retention ratio after test circulating battery 200 times, the results are shown in Table 2.
Table 2：Number is S1-S5 and the capacity retention ratio test result of the battery of D1-D5.
| Group | Capacity retention ratio (%) |
| S1 | 95 |
| S2 | 93 |
| S3 | 92 |
| S4 | 90 |
| S5 | 91 |
| D1 | 82 |
| D2 | 79 |
| D3 | 81 |
| D4 | 83 |
| D5 | 82 |
As can be seen from Table 1 and Table 2, using fluoroethylene polymer and uncrosslinked water absorbent polymer (carboxymethyl cellulose
Sodium, polyvinylpyrrolidone) be mixed to get binder production thick pole piece pattern it is relatively good, do not lose powder, it is undissolved, do not have yet
Sliver, but due to the water solubility of two macromolecule chain binders, with soaking time increase in the electrolytic solution will appear it is viscous
It ties agent and dissolves out phenomenon, pole piece is caused to soften and the decline of capacity retention ratio, and use fluoroethylene polymer and crosslinking water suction poly-
Close the thickness of object (croscarmellose sodium, crosslinking sodium polyacrylate, crosslinked polyvinylpyrrolidone) mixing bonding agent production
Pole piece does not occur the phenomenon that binder dissolution.
In addition, the pattern that fluoroethylene polymer is used alone or is crosslinked the thick pole piece that water absorbent polymer makees binder has one
Fixed defect, due to the low surface energy of PTFE, the capacity for affecting pole piece plays and cyclical stability, and is crosslinked water absorbent polymer
Cohesive force it is very low, cause thick pole piece to lose powder, phenomena such as sliver, and then the capacity for influencing thick pole piece plays and cyclical stability.
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 the specific embodiments disclosed and described above, to of the invention
Some modifications and changes should also be as falling into the scope of the claims of the present invention.In addition, although being used in this specification
Some specific terms, these terms are merely for convenience of description, does not limit the present invention in any way.
Claims (10)
1. a kind of water base compound binding agent of battery thickness pole piece, which is characterized in that by weight, include at least following component：
Fluoroethylene polymer 5-8 parts by weight；
It is crosslinked water absorbent polymer 0.5-1 parts by weight；
Water 20-40 parts by weight；
The fluoroethylene polymer and crosslinking water absorbent polymer formation intertwine with each other staggered polymer network.
2. the water base compound binding agent of battery thickness pole piece according to claim 1, it is characterised in that：The vinyl fluoride polymerization
Object is PTFE and/or PVDF.
3. the water base compound binding agent of battery thickness pole piece according to claim 1, it is characterised in that：The crosslinking water suction is poly-
Conjunction object is at least one of croscarmellose sodium, crosslinking sodium polyacrylate, crosslinked polyvinylpyrrolidone.
4. the water base compound binding agent of battery thickness pole piece according to claim 1, it is characterised in that：The vinyl fluoride polymerization
The average molecular weight of object is 600,000-80 ten thousand.
5. the water base compound binding agent of battery thickness pole piece according to claim 3, it is characterised in that：The cross-linked carboxymethyl
The average molecular weight of sodium cellulosate is 600,000-80 ten thousand, and the molecular weight of crosslinking sodium polyacrylate is 3,000,000-700 ten thousand, is crosslinked poly- second
The average molecular weight of alkene pyrrolidone is 40,000-8 ten thousand.
6. the water base compound binding agent of battery thickness pole piece according to claim 1, it is characterised in that：The crosslinking water suction is poly-
The degree of cross linking for closing object is 60%-85%.
7. a kind of battery thickness pole piece, the active material layer including collector and coated on the collection liquid surface, the active matter
Matter layer includes active material, bonding agent and conductive agent, it is characterised in that：The bonding agent is described in any one of claim 1 to 6
Bonding agent.
8. battery thickness pole piece according to claim 7, which is characterized in that the preparation method of the pole piece includes following step
Suddenly：
Crosslinking water absorbent polymer is added to the water, is sufficiently stirred by the first step, forms crosslinking water absorbent polymer solution；It again will be conductive
Agent and crosslinking water absorbent polymer solution are placed in mortar and are fully ground, and conductive agent and crosslinking water absorbent polymer is made to be formed and uniformly be led
Then active material is added in electric network, be fully ground, so that active material, conductive agent and crosslinking water absorbent polymer are formed uniformly
Conductive network and coherent network, obtain mixture；
Fluoroethylene polymer is added to the water by second step, is sufficiently stirred, and forms fluoroethylene polymer lotion；
The fluoroethylene polymer lotion of second step is added into the mixture that the first step obtains, is sufficiently stirred for third step, obtains half
Dry powder；
Half dry powder of third step is transferred on collector, tabletting by the 4th step, dry, obtains pole piece.
9. battery thickness pole piece according to claim 7, which is characterized in that the active material layer with a thickness of 1mm-2mm.
10. battery thickness pole piece according to claim 7, which is characterized in that active material, conductive agent, fluoroethylene polymer
Weight ratio with crosslinking water absorbent polymer is (75~85):(9.5~16):(5~8):(0.5~1).
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Effective date of registration: 20220920 Address after: 519070 room 703, unit 2, building 4, No. 103, Daishan Road, Xiangzhou District, Zhuhai City, Guangdong Province Patentee after: Zhao Mingxing Address before: No.1 Factory building, Maike Industrial Park, 1888 Meijing Avenue West, xiniupi village, Dalang Town, Dongguan City, Guangdong Province, 523000 Patentee before: DONGGUAN MCNAIR NEW POWER Co.,Ltd. Patentee before: DONGGUAN MCNAIR TECHNOLOGY Co.,Ltd. Patentee before: TECHNICAL INSTITUTE OF LITHIUM BATTERY ENERGY-SAVING TECHNOLOGY OF MCNAIR, DONGGUAN. |