CN109802137A - Lithium-sulfur cell binder and preparation method thereof, anode sizing agent and preparation method thereof - Google Patents
Lithium-sulfur cell binder and preparation method thereof, anode sizing agent and preparation method thereof Download PDFInfo
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- CN109802137A CN109802137A CN201811555285.XA CN201811555285A CN109802137A CN 109802137 A CN109802137 A CN 109802137A CN 201811555285 A CN201811555285 A CN 201811555285A CN 109802137 A CN109802137 A CN 109802137A
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Abstract
The present invention provides a kind of lithium-sulfur cell binders and preparation method thereof, anode sizing agent and preparation method thereof.The lithium-sulfur cell binder includes three-dimensional network macromolecular, which is obtained by carboxymethyl cellulose, polyethyleneimine and the crosslinked reaction of crosslinking agent.Using binder provided by the invention, the problem of soluble polysulfide, easy shuttle can be effectively improved, the cycle performance of battery when so as to be effectively improved sulfenyl active material as lithium sulfur battery anode material active material.
Description
Technical field
The present invention relates to battery technology fields, in particular to a kind of lithium-sulfur cell binder and preparation method thereof, just
Pole slurry and preparation method thereof.
Background technique
With the rapid development of electronic equipment, electric car, Space Facilities, increasingly higher demands are proposed to battery,
There is high-energy-density, low cost, environmental-friendly battery to have very important significance for development.Lithium-sulfur cell is lithium ion battery
In important a member, specific capacity is up to 1675mAh/g, and specific energy density is up to 2500Wh/kg, is current commercial Li-ion
4 to 5 times of battery theoretical specific capacity, have broad application prospects.
However, lithium-sulfur cell is in moving towards commercialization process, there are still following problems: (1) active material S and reaction produce
Object Li2Sx(x=1,2) poorly conductive；(2) the more lithium sulfide Li of intermediate product2Sx(4≤x≤8) are soluble in electrolyte, are formed
Shuttle effect；(3) S simple substance is changed into Li2Sx(x=1,2) volume expansion is up to 80% when；Due to the above problems, lithium sulphur
For battery in charge and discharge process, it is low that there are specific discharge capacities, the phenomenon of cyclical stability difference.
Binder is by the way that active material, conductive agent and collector to be adhered to each other, to keep the machinery of pole piece structure
The reliability of stability and conductive network shrinks volume expansion severe lithium-sulfur cell, is one of key component.So
And it is also less for the research of lithium-sulfur cell binder at present, the binder being widely used in lithium-sulfur cell at present is linear
High molecular polymer PVDF, on the one hand, its physical adhesive attraction is easy ageing failure in lithium-sulfur cell recycles for a long time, separately
Outside, PVDF can not cope with present in lithium-sulfur cell the defect that this more lithium sulfides are soluble, easily shuttle.Therefore, PVDF is not
The performance of lithium-sulfur cell can be promoted very well.
Based on the above reasons, it is necessary to a kind of new binder be provided, it is made to better solve more vulcanizations in lithium-sulfur cell
The problem of object is soluble, easy shuttle, and then improve the cycle performance of battery.
Summary of the invention
The main purpose of the present invention is to provide a kind of lithium-sulfur cell binder and preparation method thereof, anode sizing agent and its systems
Preparation Method, with solve in the prior art lithium-sulfur cell because polysulfide is soluble, cycle performance of battery difference caused by easy shuttle
Problem.
To achieve the goals above, according to an aspect of the invention, there is provided a kind of lithium-sulfur cell binder comprising
Three-dimensional network macromolecular, three-dimensional network macromolecular are obtained by carboxymethyl cellulose, polyethyleneimine and the crosslinked reaction of crosslinking agent.
Further, the average molecular mass of carboxymethyl cellulose is 800~1200, and polyethyleneimine is divided equally again
Son amount is 3000~3500.
Further, the weight ratio between carboxymethyl cellulose and polyethyleneimine is 1:(0.3~2), more preferably 1:
(1~1.5).
Further, crosslinking agent is glutaraldehyde, and the weight of crosslinking agent is preferably denoted as A, by carboxymethyl cellulose and poly- second
The total weight of alkene imines is denoted as B, and A/B=(0.1~0.3): 1, more preferable A/B=(0.15~0.2): 1.
According to another aspect of the present invention, a kind of preparation method of lithium-sulfur cell binder is additionally provided comprising following
Step: carboxymethyl cellulose, polyethyleneimine, crosslinking agent and solvent are mixed to get raw material mixed liquor；To raw material mixed liquor into
Row cross-linking reaction obtains lithium-sulfur cell binder.
Further, in raw material mixed liquor, the mass concentration of carboxymethyl cellulose is 3.2~5.0%, polyethyleneimine
Mass concentration is 1.0~10%.
Further, the temperature of cross-linking reaction is 20~30 DEG C, it is preferable that the solvent is water.
The another aspect provided according to the present invention additionally provides a kind of anode sizing agent comprising sulfenyl active material, conduction
Agent and above-mentioned lithium-sulfur cell binder.
The another aspect provided according to the present invention, and provide a kind of preparation method of above-mentioned anode sizing agent comprising with
Lower step: using carboxymethyl cellulose, polyethyleneimine, crosslinking agent and solvent as the raw material of lithium-sulfur cell binder, by lithium sulphur
After raw material, sulfenyl active material and the conductive agent of battery binder mix, crosslinked reaction obtains anode sizing agent.
Further, during the raw material of lithium-sulfur cell binder, sulfenyl active material and conductive agent being mixed,
Crosslinking agent is added by the way of dropwise addition, crosslinked reaction obtains anode sizing agent.
Lithium-sulfur cell binder provided by the invention includes three-dimensional network macromolecular, and three-dimensional network macromolecular is by carboxymethyl fibre
Dimension element, polyethyleneimine and the crosslinked reaction of crosslinking agent obtain.Using binder provided by the invention, more sulphur can be effectively improved
The problem of compound is soluble, easy shuttle, so as to be effectively improved sulfenyl active material as lithium sulfur battery anode material activity
Cycle performance of battery when substance.
Lithium-sulfur cell bonding of the invention can be prepared in the preparation method of lithium-sulfur cell binder provided by the invention
Agent.
The preparation method of anode sizing agent provided by the invention available sulfenyl active material and is led using being cross-linked in situ
Electric agent is uniformly distributed in the anode sizing agent in three-dimensional network macromolecular binder.
Contain three-dimensional network macromolecular in anode sizing agent provided by the invention, is prepared into anode for after lithium-sulfur cell, energy
The problem of being enough effectively improved soluble polysulfide, easy shuttle.
Specific embodiment
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.Below in conjunction with embodiment, the present invention will be described in detail.
As described in background of invention part, the lithium-sulfur cell of the prior art exists because polysulfide is readily soluble
The problem of solution, the caused cycle performance of battery difference that easily shuttles.
To solve the above-mentioned problems, the present invention provides a kind of lithium-sulfur cell binders comprising three-dimensional network macromolecular,
The three-dimensional network macromolecular is obtained by carboxymethyl cellulose (CMC), polyethyleneimine (PEI) and the crosslinked reaction of crosslinking agent.
The binder when binder can be used as lithium-sulphur cell positive electrode production uses, by the way that binder, sulfenyl is active
Material and conductive agent mixing, are coated on a current collector, dry, can form the anode of lithium-sulfur cell.Carboxylic in binder raw material
Methylcellulose and polyethyleneimine can crosslink reaction under the action of crosslinking agent and form three-dimensional network macromolecular.It is this
Three-dimensional network macromolecular skeleton can bind polysulfide, and numerous polar groups (such as the amino carried on molecule
Group) polysulfide can also be adsorbed, it prevents its dissolution in the electrolyte, more avoids it and shuttle effect occurs to enter battery negative
Pole.The problem of above reason enables binder provided by the invention to be effectively improved soluble polysulfide, easy shuttle, thus
Cycle performance of battery of the sulfenyl active material as lithium sulfur battery anode material active material when can be effectively improved.
It should be noted that binder of the invention can select following manner in storage and use: (1) by three dimensional network
The binder of network macromolecular mixes three-dimensional network macromolecular, positive electrode active materials, conductive agent and solvent when being kept separately use
Prepare anode sizing agent；(2) the binder dissolution of three-dimensional network macromolecular is saved in a solvent, preferably water makees solvent, in use,
Positive electrode active materials, conductive agent and solvent are added in the solution of binder；(3) by carboxymethyl cellulose, polyethyleneimine and
Solvent is configured to mixed solution and individually stores and transport, and crosslinking agent is individually stored and transported, be in the specific use process,
Crosslinking agent is added in mixed solution to the binder for crosslinking reaction and forming three-dimensional network macromolecular.
In a preferred embodiment, the average molecular mass of carboxymethyl cellulose is 800~1200, poly- second
The weight average molecular weight of alkene imines is 3000~3500.By control carboxymethyl cellulose average molecular mass be 800~
1200, the weight average molecular weight of polyethyleneimine is 3000~3500, so that the three-dimensional network macromolecular is with preferably flexible
And mechanical property, the volume change of sulphur in cyclic process can be adapted to by the Flexible change of strand, and can more bear volume
The stress variation of dilation, to be conducive to the cycle performance for further improving battery.
Wherein, the average molecular mass of carboxymethyl cellulose it is typical but without limitation preferably 800,900,1000,
1100 and 1200, the weight average molecular weight of polyethyleneimine it is typical but without limitation preferably 3000,3100,3200,3300,
3400 and 3500.
In order to further increase the volumetric stress ability to bear of the three-dimensional network macromolecular formed after binder crosslinking curing,
Binding and adsorption capacity of the macromolecular to polysulfide are further increased simultaneously, it is in a preferred embodiment, above-mentioned viscous
Tying the weight ratio in agent between carboxymethyl cellulose and polyethyleneimine is 1:(0.3~2).More preferable carboxymethyl cellulose and poly-
Weight ratio between aziridine is 1:(1~1.5).In the range by the weight ratio control of the two, three dimensional network can be adjusted
On the one hand the structure of network macromolecular has the segment between each crosslinking points more fully flexible, separately to state preferably
On the one hand be conducive to adjust three-dimensional net structure " mesh " size, can more fully bind polysulfide, while advantageous
Enter in electrolyte and reacted with positive electrode, keeps efficiency for charge-discharge.Meanwhile the network structure of three-dimensional network macromolecular
It is more stable, to be more advantageous to the cycle performance of battery and capacity stability for improving lithium-sulfur cell.
Wherein, the weight ratio between carboxymethyl cellulose and polyethyleneimine is typical but preferred without limitation 1:0.3,1:
0.4,1:0.5,1:0.6,1:0.7,1:0.8,1:0.9,1:1,1:1.2,1:1.3,1:1.5,1:1.8 and 1:2.
Preferably, above-mentioned solvent is water.Carboxymethyl cellulose, polyethyleneimine are water-soluble polymer, in water can
Enough form good dissolution.In addition, using water as the feature of environmental protection that solvent also advantageously improves binder, organic solvent is avoided
Injury to human body and environment has wider application prospect.Preferably, above-mentioned binder is in situ by the raw material of binder
Crosslinking is made.Using being cross-linked in situ, it can be conductive agent and active material and form good dispersion in a binder.
Preferably, above-mentioned crosslinking agent is glutaraldehyde.There are two the carbonylic carbon atoms of band part positive electricity on glutaraldehyde molecules, hold
Easily and on carboxymethyl cellulose there are the amido N atoms of lone pair electrons pair on electronegative hydroxyl oxygen atom and polyethyleneimine
Therefore necleophilic reaction, which occurs, individually can crosslink reaction with carboxymethyl cellulose, polyethyleneimine respectively, can also be simultaneously
Reaction is crosslinked with carboxymethyl cellulose, polyethyleneimine, key reaction principle is as follows:
Three kinds of cross-linked polymers of above-mentioned generation (- COO- and-NH under electrostatic interaction3+Between there are electrostatic attraction effects)
Be self-assembly of that stability is more preferable, the better three-dimensional network molecular structure of mechanical property, for inhibit polysulfide dissolution and
Shuttling has better facilitation, to be conducive to further improve cycle performance of battery.Preferably, by the weight of crosslinking agent
It is denoted as A, the total weight of carboxymethyl cellulose and polyethyleneimine is denoted as B, A/B=(0.1~0.3): 1, more preferable A/B=
(0.15~0.2): 1.
Wherein, A/B is typical but preferred without limitation 0.1:1,0.15:1,0.18:1,0.2:1,0.25:1 and 0.3:1.
According to another aspect of the present invention, a kind of preparation method of above-mentioned binder is provided comprising following steps: will
Carboxymethyl cellulose, polyethyleneimine, crosslinking agent and solvent are mixed to get raw material mixed liquor；Raw material mixed liquor be crosslinked anti-
It answers, obtains lithium-sulfur cell binder.In the binder being prepared by the method, contain carboxymethyl cellulose and polyethyleneimine
The three-dimensional network macromolecular that reaction is formed is crosslinked under the action of crosslinking agent.This three-dimensional network macromolecular skeleton can be right
Polysulfide is bound, and the numerous polar groups (such as amino group) carried on molecule can also adsorb polysulfide,
It prevents its dissolution in the electrolyte, more avoids its generation shuttle effect and enter battery cathode.The above reason proposes the present invention
The binder of confession can be effectively improved the problem of soluble polysulfide, easy shuttle, so as to be effectively improved sulfenyl activity material
Cycle performance of battery when expecting as lithium sulfur battery anode material active material.
In order to improve the coating performance of binder, while see below sulfenyl active material and conductive agent (
Text) it better disperses wherein, in a preferred embodiment, the quality of carboxymethyl cellulose is dense in above-mentioned raw materials mixed liquor
Degree is 3.2~5.0%, and the mass concentration of polyethyleneimine is 1.0~10%.Above-mentioned cross-linking reaction can carry out at normal temperature,
It is preferred that the temperature of above-mentioned cross-linking reaction is 20~30 DEG C.Crosslinking agent, side stirring can be added in cross-linking process in a manner of dropwise addition
Side is added dropwise.
Wherein, in raw material mixed liquor the mass concentration of carboxymethyl cellulose it is typical but without limitation preferably 3.2%,
3.5%, 3.8%, 4.0%, 4.2%, 4.5%, 4.8% and 5.0%.
Wherein, in raw material mixed liquor the mass concentration of polyethyleneimine it is typical but without limitation preferably 1.0%, 2%,
3%, 4%, 5%, 6%, 7%, 8%, 9% and 10%.
Wherein, the temperature typical case of cross-linking reaction but without limitation preferably 20 DEG C, 22 DEG C, 25 DEG C, 27 DEG C and 30 DEG C.
It should be noted that first carboxymethyl cellulose, polyethyleneimine and solvent can also be mixed in the preparation method
It closes；Mixed liquor can be stored or be transported, and crosslinking agent and mixed liquor are stored separately or transport；In the specific use process, will
Crosslinking agent is added mixed liquor and carries out cross-linked polymeric.
According to another aspect of the present invention, provide a kind of anode sizing agent comprising sulfenyl active material, conductive agent and on
State lithium-sulfur cell binder.In actual application, which is that lithium-sulphur cell positive electrode prepares raw material, by by its
It is coated on after being dried on plus plate current-collecting body, the active material of lithium-sulphur cell positive electrode can be formed.As it was noted above, due to viscous
Carboxymethyl cellulose and polyethyleneimine in knot agent can crosslink reaction under the action of crosslinking agent and form three-dimensional network
Macromolecular, numerous polar groups that this three-dimensional network macromolecular skeleton can bind polysulfide, and carry on molecule
Polysulfide can also be adsorbed in group, prevent its dissolution in the electrolyte, more avoid its generation shuttle effect and enter battery cathode.
For these reasons, the active material formed using the anode sizing agent, is applied to lithium sulphur as lithium-sulphur cell positive electrode active material
The cycle performance for the battery that can be effectively improved when battery.
Preferably, by weight, be 60~80 parts including sulfenyl active material in anode sizing agent, conductive agent is 4~40
Part, 2~20 parts of lithium-sulfur cell binder.
Above-mentioned sulfenyl active material can be the common sulfenyl active material in the field, for example can be sulphur simple substance, can also
With the composite material for being sulphur simple substance and adhesive is mixed to form, adhesive can be polyacrylonitrile etc..In addition, sulfenyl active material
It is also possible to CNT/S composite material, S/C composite material or S/PAN composite material, the electrically conductive carbon black of conductive agent, carbon nanotube
(CNT), one of super P or a variety of.
According to another aspect of the invention, a kind of preparation method of above-mentioned anode sizing agent is additionally provided comprising following step
It is rapid: using carboxymethyl cellulose, polyethyleneimine, crosslinking agent and solvent as the raw material of lithium-sulfur cell binder, by lithium-sulfur cell
After raw material, sulfenyl active material and the conductive agent of binder mix, crosslinked reaction obtains anode sizing agent.Using this method,
Preparatory dispersion is formed after in advance mixing sulfenyl active material, conductive agent with the raw material of binder in manufacturing process, is then passed through
It is cross-linked in situ (crosslinking condition is crosslinking condition described previously), sulfenyl active material and conductive agent can be promoted in a binder
Dispersion, after crosslinking to be done, sulfenyl active material and conductive agent can preferably be bound by three-dimensional network macromolecular, to have
Conducive to the cycle performance for further increasing battery.After drying, active material layer can be formed.
In a preferred embodiment, during the raw material of active material being mixed, using the side of dropwise addition
Crosslinking agent is added in formula, obtains anode sizing agent.Material can be made more fully to mix dispersion to stir in charging during dropwise addition.
During being actually added into, crosslinking agent can be dissolved in solvent in advance, be then added in the form of solvent, be conducive to be crosslinked
Agent spreads more evenly across.
According to another aspect of the present invention, it is further provided a kind of lithium-sulfur cell, including anode, the anode include anode
Collector and active material positioned at its surface, the active material are that above-mentioned anode sizing agent is coated, drying obtains.Before being based on
Every reason described in text, lithium-sulfur cell provided by the invention have better cycle performance, have extensive reference prospect.?
When practical application, above-mentioned plus plate current-collecting body can select material commonly used in the art, such as aluminium foil etc..
The application is described in further detail below in conjunction with specific embodiment, these embodiments should not be understood as limitation originally
Apply for range claimed.
Following sulfenyl active material used in the examples the preparation method is as follows:
After taking 2g sublimed sulfur, 1g Ketjen black ball milling mixing, it is subsequently placed into closed container, heats 12h at 155 DEG C, obtain
To S/C compound.
Embodiment 1
20g distilled water is taken, is added 1g carboxymethyl cellulose (CMC, average molecular mass 800~1200), through machinery
Uniform CMC aqueous solution is obtained after stirring；Then the polyethyleneimine that 1g mass concentration is 30% is continuously added to CMC aqueous solution
(PEI, weight average molecular mass 3000~3500) aqueous solution, obtains evenly dispersed CMC-PEI mixed solution through mechanical stirring
(CMC:PET mass ratio 1:0.3).
Take 2g S/C compound, 0.25g CNT (carbon nanotube) and 4.231g CMC-PEI mixed solution (CMC-PEI
Account for the 10% of three's total material dry weight), it is ground uniformly after, dropwises addition mass concentration be 10% glutaraldehyde water solution 0.5g,
High-speed stirred is carried out after being cross-linked in situ at 25 DEG C of room temperature to slurry during dropwise addition and obtains anode sizing agent.
Gained anode sizing agent is coated on aluminium foil, forms lithium-sulphur cell positive electrode after drying 12h at 60 DEG C.
Embodiment 2
20g distilled water is taken, is added 1g carboxymethyl cellulose (CMC, average molecular mass 800~1200), through machinery
Uniform CMC aqueous solution is obtained after stirring；Then the polyethylene that 3.333g mass concentration is 30% is continuously added to CMC aqueous solution
It is molten to obtain evenly dispersed CMC-PEI mixing through mechanical stirring for imines (PEI, weight average molecular mass 3000~3500) aqueous solution
Liquid (CMC:PET mass ratio 1:1).
Take 2g S/C compound, 0.25g CNT (carbon nanotube) and 3.042g CMC-PEI mixed solution (CMC-PEI
Account for the 10% of three's total material dry weight), it is ground uniformly after, dropwises addition mass concentration be 10% glutaraldehyde water solution 0.5g,
High-speed stirred is carried out after being cross-linked in situ at 25 DEG C of room temperature to slurry during dropwise addition and obtains anode sizing agent.
Gained anode sizing agent is coated on aluminium foil, forms lithium-sulphur cell positive electrode after drying 12h at 60 DEG C.
Embodiment 3
20g distilled water is taken, is added 1g carboxymethyl cellulose (CMC, average molecular mass 800~1200), through machinery
Uniform CMC aqueous solution is obtained after stirring；Then the polyethyleneimine that 5g mass concentration is 30% is continuously added to CMC aqueous solution
(PEI, weight average molecular mass 3000~3500) aqueous solution, obtains evenly dispersed CMC-PEI mixed solution through mechanical stirring
(CMC:PET mass ratio 1:1.5).
Take 2g S/C compound, 0.25g CNT (carbon nanotube) and 2.038g CMC-PEI mixed solution (CMC-PEI
Account for the 8% of three's total material dry weight), it is ground uniformly after, dropwises addition mass concentration be 10% glutaraldehyde water solution 0.5g, drip
High-speed stirred is carried out after being cross-linked in situ at 25 DEG C of room temperature to slurry during adding and obtains anode sizing agent.
Gained anode sizing agent is coated on aluminium foil, forms lithium-sulphur cell positive electrode after drying 12h at 60 DEG C.
Embodiment 4
20g distilled water is taken, is added 1g carboxymethyl cellulose (CMC, average molecular mass 800~1200), through machinery
Uniform CMC aqueous solution is obtained after stirring；Then the polyethyleneimine that 5g mass concentration is 30% is continuously added to CMC aqueous solution
(PEI, weight average molecular mass 3000~3500) aqueous solution, obtains evenly dispersed CMC-PEI mixed solution through mechanical stirring
(CMC:PET mass ratio 1:1.5).
Take 2g S/C compound, 0.25g CNT (carbon nanotube) and 1.232g CMC-PEI mixed solution (CMC-PEI
Account for the 5% of three's total material dry weight), it is ground uniformly after, dropwises addition mass concentration be 10% glutaraldehyde water solution 0.5g, drip
High-speed stirred is carried out after being cross-linked in situ at 25 DEG C of room temperature to slurry during adding and obtains anode sizing agent.
Gained anode sizing agent is coated on aluminium foil, forms lithium-sulphur cell positive electrode after drying 12h at 60 DEG C.
Embodiment 5
20g distilled water is taken, is added 1g carboxymethyl cellulose (CMC, average molecular mass 800~1200), through machinery
Uniform CMC aqueous solution is obtained after stirring；Then the polyethylene that 6.667g mass concentration is 30% is continuously added to CMC aqueous solution
It is molten to obtain evenly dispersed CMC-PEI mixing through mechanical stirring for imines (PEI, weight average molecular mass 3000~3500) aqueous solution
Liquid (CMC:PET mass ratio 1:2).
Taking 2g S/C compound, 0.25g CNT (carbon nanotube) and 2.25g CMC-PEI mixed solution, (CMC-PEI is accounted for
The 10% of three's total material dry weight), it is ground uniformly after, dropwises addition mass concentration be 10% glutaraldehyde solution 0.5g, dropwise addition
High-speed stirred is carried out after being cross-linked in situ at 25 DEG C of room temperature to slurry in the process and obtains anode sizing agent.
Gained anode sizing agent is coated on aluminium foil, forms lithium-sulphur cell positive electrode after drying 12h at 60 DEG C.
Embodiment 6
20g distilled water is taken, is added 1g carboxymethyl cellulose (CMC, weight average molecular mass 800~1200), through mechanical stirring
Uniform CMC aqueous solution is obtained afterwards；Then the polyethyleneimine that 0.667g mass concentration is 30% is continuously added to CMC aqueous solution
(PEI, weight average molecular mass 3000~3500) aqueous solution, obtains evenly dispersed CMC-PEI mixed solution through mechanical stirring
(CMC:PET mass ratio 1:0.2).
Taking 2g S/C compound, 0.25g CNT (carbon nanotube) and 4.51g CMC-PEI mixed solution, (CMC-PEI is accounted for
The 10% of three's total material dry weight), it is ground uniformly after, dropwises addition mass concentration be 10% glutaraldehyde solution 0.5g, dropwise addition
High-speed stirred is carried out after being cross-linked in situ at 25 DEG C of room temperature to slurry in the process and obtains anode sizing agent.
Gained anode sizing agent is coated on aluminium foil, forms lithium-sulphur cell positive electrode after drying 12h at 60 DEG C.
Embodiment 7
20g distilled water is taken, is added 1g carboxymethyl cellulose (CMC, average molecular mass 800~1200), through machinery
Uniform CMC aqueous solution is obtained after stirring；Then the polyethylene that 3.333g mass concentration is 30% is continuously added to CMC aqueous solution
It is molten to obtain evenly dispersed CMC-PEI mixing through mechanical stirring for imines (PEI, weight average molecular mass 3000~3500) aqueous solution
Liquid (CMC:PET mass ratio 1:1).
Take 2g S/C compound, 0.25g CNT (carbon nanotube) and 3.042g CMC-PEI mixed solution (CMC-PEI
Account for the 10% of three's total material dry weight), it is ground uniformly after, dropwises addition mass concentration be 10% glutaraldehyde water solution
0.375g carries out high-speed stirred after being cross-linked in situ at 25 DEG C of room temperature to slurry during dropwise addition and obtains anode sizing agent.
Gained anode sizing agent is coated on aluminium foil, forms lithium-sulphur cell positive electrode after drying 12h at 60 DEG C.
Embodiment 8
20g distilled water is taken, is added 1g carboxymethyl cellulose (CMC, average molecular mass 800~1200), through machinery
Uniform CMC aqueous solution is obtained after stirring；Then the polyethylene that 3.333g mass concentration is 30% is continuously added to CMC aqueous solution
It is molten to obtain evenly dispersed CMC-PEI mixing through mechanical stirring for imines (PEI, weight average molecular mass 3000~3500) aqueous solution
Liquid (CMC:PET mass ratio 1:1).
Take 2g S/C compound, 0.25g CNT (carbon nanotube) and 3.042g CMC-PEI mixed solution (CMC-PEI
Account for the 10% of three's total material dry weight), it is ground uniformly after, dropwises addition mass concentration be 10% glutaraldehyde water solution 0.25g,
High-speed stirred is carried out after being cross-linked in situ at 25 DEG C of room temperature to slurry during dropwise addition and obtains anode sizing agent.
Gained anode sizing agent is coated on aluminium foil, forms lithium-sulphur cell positive electrode after drying 12h at 60 DEG C.
Embodiment 9
20g distilled water is taken, is added 1g carboxymethyl cellulose (CMC, average molecular mass 800~1200), through machinery
Uniform CMC aqueous solution is obtained after stirring；Then the polyethylene that 3.333g mass concentration is 30% is continuously added to CMC aqueous solution
It is molten to obtain evenly dispersed CMC-PEI mixing through mechanical stirring for imines (PEI, weight average molecular mass 3000~3500) aqueous solution
Liquid (CMC:PET mass ratio 1:1).
Take 2g S/C compound, 0.25g CNT (carbon nanotube) and 3.042g CMC-PEI mixed solution (CMC-PEI
Account for the 10% of three's total material dry weight), it is ground uniformly after, dropwises addition mass concentration be 10% glutaraldehyde water solution 0.75g,
High-speed stirred is carried out after being cross-linked in situ at 25 DEG C of room temperature to slurry during dropwise addition and obtains anode sizing agent.
Gained anode sizing agent is coated on aluminium foil, forms lithium-sulphur cell positive electrode after drying 12h at 60 DEG C.
Comparative example 1
Using PVDF as binder, take that 2g S/C compound, (PVDF accounts for total material to 0.25g CNT and 0.25g PVDF
Mass ratio 10%), it is uniform that NMP (N-Methyl pyrrolidone) grinding is added.Finally, gained anode sizing agent is coated on aluminium foil,
Lithium-sulphur cell positive electrode is formed after drying.
Performance detection:
By anode of the anode as lithium-sulfur cell obtained in each embodiment and comparative example, diaphragm use Celgard2400,
Cathode uses lithium piece, electrolyte composition for (1M LITFSI+DOL/DME+2wt%LiNO3), button is assembled into glove box
Battery detecting battery performance: the cycle performance of button electricity is tested under 25 DEG C, 0.1C multiplying power with blue electric tester, as a result such as 1 institute of table
Show:
Table 1
It can be seen from the above description that the above embodiments of the present invention realized the following chievements: the present invention mentions
The binder of confession can be effectively improved the problem of soluble polysulfide, easy shuttle, so as to be effectively improved sulfenyl activity material
Cycle performance of battery when expecting as lithium sulfur battery anode material active material.
Specifically, in embodiment 1 to 5, by the weight ratio in binder between carboxymethyl cellulose and polyethyleneimine
For 1:(0.3~2), it is more advantageous to the flexible and mechanical property for improving three-dimensional network macromolecular, is also made it have preferably
" mesh " size, can further increase lithium-sulfur cell cycle performance of battery and capacity stability (cycle-index be 1 time when pair
The specific capacity answered is higher, shows that the circulation volume for the first time of battery is higher, and with the increase of cycle-index, battery specific capacity is reduced
It is fewer, show that capacity stability is higher, cycle performance of battery is better).It more particularly, will be in binder in embodiment 2 to 4
Weight ratio between carboxymethyl cellulose and polyethyleneimine is 1:(1~1.5), the cycle performance of battery is more preferably.
In addition to this, by the data in embodiment 2,7 to 9 it is found that the weight of crosslinking agent is denoted as A, by carboxymethyl cellulose
The total weight of element and polyethyleneimine is denoted as B, and when A/B=(0.15~0.2): when 1, the cycle performance of battery is more preferably.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of lithium-sulfur cell binder, which is characterized in that the binder includes three-dimensional network macromolecular, the three-dimensional network
Macromolecular is obtained by carboxymethyl cellulose, polyethyleneimine and the crosslinked reaction of crosslinking agent.
2. lithium-sulfur cell binder according to claim 1, which is characterized in that being averaged for the carboxymethyl cellulose is opposite
Molecular mass is 800~1200, and the weight average molecular weight of the polyethyleneimine is 3000~3500.
3. lithium-sulfur cell binder according to claim 2, which is characterized in that the carboxymethyl cellulose and the poly- second
Weight ratio between alkene imines is 1:(0.3~2), more preferably 1:(1~1.5).
4. lithium-sulfur cell binder according to any one of claim 1 to 3, which is characterized in that the crosslinking agent is penta
The weight of the crosslinking agent is preferably denoted as A by dialdehyde, and the total weight of the carboxymethyl cellulose and the polyethyleneimine is remembered
For B, A/B=(0.1~0.3): 1, more preferable A/B=(0.15~0.2): 1.
5. a kind of preparation method of lithium-sulfur cell binder described in any one of Claims 1-4, which is characterized in that including
Following steps:
Carboxymethyl cellulose, polyethyleneimine, crosslinking agent and solvent are mixed to get raw material mixed liquor；
Cross-linking reaction is carried out to the raw material mixed liquor, obtains the lithium-sulfur cell binder.
6. preparation method according to claim 5, which is characterized in that in the raw material mixed liquor, the carboxymethyl cellulose
The mass concentration of element is 3.2~5.0%, and the mass concentration of the polyethyleneimine is 1.0~10%.
7. preparation method according to claim 5, which is characterized in that the temperature of the cross-linking reaction is 20~30 DEG C, excellent
Solvent described in selection of land is water.
8. a kind of anode sizing agent, which is characterized in that the anode sizing agent includes sulfenyl active material, conductive agent and claim 1
To lithium-sulfur cell binder described in any one of 4.
9. a kind of preparation method of anode sizing agent according to any one of claims 8, which comprises the following steps:
Using carboxymethyl cellulose, polyethyleneimine, crosslinking agent and solvent as the raw material of lithium-sulfur cell binder, by the lithium sulphur
After raw material, sulfenyl active material and the conductive agent of battery binder mix, crosslinked reaction obtains the anode sizing agent.
10. preparation method according to claim 9, which is characterized in that by the raw material of the lithium-sulfur cell binder, described
During sulfenyl active material and the conductive agent are mixed, the crosslinking agent is added by the way of dropwise addition, through described
Cross-linking reaction obtains the anode sizing agent.
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