CN109768283A - A kind of silicon-based anode binder and preparation method thereof - Google Patents
A kind of silicon-based anode binder and preparation method thereof Download PDFInfo
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- CN109768283A CN109768283A CN201910040121.1A CN201910040121A CN109768283A CN 109768283 A CN109768283 A CN 109768283A CN 201910040121 A CN201910040121 A CN 201910040121A CN 109768283 A CN109768283 A CN 109768283A
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Abstract
The present invention provides a kind of silicon-based anode binder, and the binder is the amphipathic nature block polymer organic acid modified by fluoro, and the block copolymer is obtained by two kinds of previously prepared obtained different polymer reactions.The expansion of silicon-based anode can be effectively suppressed in the binder, and silicium cathode battery is made to show good cycle performance.The preparation method simple synthetic method, simple process are suitable for industrialized production.
Description
Technical field
The invention belongs to battery material fields, are related to a kind of negative electrode binder more particularly to a kind of silicon-based anode binder
And preparation method thereof.
Background technique
With the rise of new-energy automobile, power battery already becomes new-energy automobile key components and parts, and power battery is
The field that layout is even unfolded is paid close attention to as vehicle factor.Compared with conventional fuel oil car, electric vehicle is more environmentally-friendly, also
To the support energetically of country, Ministry of Industry and Information and the Committee of Development and Reform are printed and distributed according to notice, arrive the year two thousand twenty, power battery monomer specific energy will reach
300wh/kg will reach so high energy density, and conventional graphite cathode is helpless, currently, more real scheme
Silicon-based anode is exactly selected, in comparison, the theoretical gram volume of silicon materials is up to 4200mAh/g (Li4.4Si).In addition, silicon
Embedding lithium platform (0.2V vs.Li+/Li) is higher than graphite, and security performance is higher, rich reserves, environmental-friendly.
Using the advantage of silicon-based anode it is clear that however, in actual application, most important defect is: silicon substrate
Again during charge and discharge cycles, volume constantly expands cathode, and highest is expandable to 300%, causes negative electrode active material rupture point
Change, with electrolyte contacts, SEI is constantly crushed reconstruct, consumes a large amount of electrolyte, impedance becomes larger, the continuous cracking of cycle performance, most
Lead to battery failure eventually.To solve the above-mentioned problems, scientific research personnel takes alloying, the means such as nanosizing and cladding, or
The volume expansion of silicium cathode is inhibited by binder matching, the volume that above-mentioned measure alleviates silicon-based anode to a certain extent is swollen
It is swollen, but requirement is also much not achieved.
It is negative that 107611344 A of CN discloses a kind of dual cross-linked binder of lithium battery silicon based anode material, lithium battery silicon substrate
Pole material and preparation method, battery cathode and lithium battery.The dual cross-linked binder, including polyacrylic acid and diisocyanate
Ester, the binder is by being added into diisocyanate, under room temperature, realizes that the carboxyl of diisocyanate and polyacrylic acid occurs
Polycondensation reaction, the polymeric binder with network structure formed to polyacrylic acid play further firm effect, realize
Dual crosslinking.But the dual cross-linked binder of the technical solution is poor to the expansion inhibition of silicon-based anode, throws away and deposits in safety
In problem.
Summary of the invention
To solve the technical problems existing in the prior art, the present invention provides a kind of silicon-based anode binder and its preparation side
The expansion of silicon-based anode can be effectively suppressed in method, the binder, and silicium cathode battery is made to show good cycle performance.
In order to achieve the above object, the invention adopts the following technical scheme:
It is an object of the present invention to provide a kind of silicon-based anode binder, the binder is organic acid modified by fluoro
Amphipathic nature block polymer.
As currently preferred technical solution, the raw material of the binder includes: block copolymer 4 in parts by weight
~10 parts, 30~50 parts of 4~10 parts of fluoro organic acid and the first solvent.
Wherein, the parts by weight of block copolymer can be 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts etc., and fluoro is organic
The parts by weight of acid can be 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts etc., and the mass parts of the first solvent can be 30 parts, 32
Part, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 parts or 50 parts etc., it is not limited to cited numerical value, above-mentioned each numerical value
Other unlisted numerical value are equally applicable in range.
As currently preferred technical solution, the raw material for synthesizing the block copolymer in parts by weight includes:
8~10 parts of one 5~9 parts of polymer, 5~10 parts of second polymer and the second solvent.
Wherein, the parts by weight of first polymer can be 5 parts, 6 parts, 7 parts, 8 parts or 9 parts etc., the weight of second polymer
Part can be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts etc., and the parts by weight of the second solvent can be 8 parts, 8.2 parts, 8.5 parts, 8.8
Part, 9 parts, 9.2 parts, 9.5 parts, 9.8 parts or 10 parts etc., it is not limited to cited numerical value, in above-mentioned each numberical range its
His unlisted numerical value is equally applicable.
As currently preferred technical solution, the raw material for synthesizing the first polymer in parts by weight includes:
One 7~10 parts of polymerized monomer, the first 1~4 part of complexing agent, 1~3 part of stannous chloride, the first 0.05~0.1 part of initiator and
Three 7~10 parts of solvents.
Wherein, the parts by weight of the first polymerized monomer can be 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts or 10 parts etc.,
The parts by weight of first complexing agent can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts or 4 parts etc., the parts by weight of stannous chloride
It can be 1 part, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts, 2.8 parts or 3 parts etc., the parts by weight of the first initiator can
To be 0.05 part, 0.06 part, 0.07 part, 0.08 part, 0.09 part or 0.1 part etc., the parts by weight of third solvent can be 7 parts, 7.5
Part, 8 parts, 8.5 parts, 9 parts, 9.5 parts or 10 parts etc., it is not limited to cited numerical value, in above-mentioned each numberical range other
Unlisted numerical value is equally applicable.
Preferably, the raw material for synthesizing the second polymer in parts by weight includes: 6~10 parts of the second polymerized monomer,
Second 2~5 parts of complexing agent, 1~3 part of copper chloride, 0.05~0.4 part of copper powder, the second 0.05~0.2 part of initiator and the 4th molten
6~10 parts of agent.
Wherein, the parts by weight of the second polymerized monomer can be 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5
Part or 10 parts etc., the parts by weight of the second complexing agent can be 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts or 5 parts etc., chlorination
The parts by weight of copper can be 1 part, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts, 2.8 parts or 3 parts etc., the second initiator
Parts by weight can be 0.05 part, 0.06 part, 0.08 part, 0.1 part, 0.12 part, 0.15 part, 0.18 part or 0.2 part etc., the 4th is molten
The mass parts of agent can be 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts or 10 parts etc., it is not limited to
Cited numerical value, other interior unlisted numerical value of above-mentioned each numberical range are equally applicable.
As currently preferred technical solution, first polymerized monomer include Tert-butyl Methacrylate, acrylonitrile,
In methyl methacrylate, tert-butyl acrylate or n-isopropyl acrylamide any one or at least two combination, institute
It states combination typical case but non-limiting example has: combination, acrylonitrile and the methacrylic acid of Tert-butyl Methacrylate and acrylonitrile
The combination of methyl esters, the combination of methyl methacrylate and tert-butyl acrylate, tert-butyl acrylate and n-isopropyl acrylamide
Combination, n-isopropyl acrylamide and the combination or Tert-butyl Methacrylate of Tert-butyl Methacrylate, acrylonitrile and first
The combination etc. of base methyl acrylate.
Preferably, first ligand include three (2- dimethylaminoethyl) amine, 4,4 '-dinonyl -2,2 '-bipyridyls or
In pentamethyl-diethylenetriamine any one or at least two combination, the combination is typical but non-limiting example has: three
(2- dimethylaminoethyl) amine and the combination of 4,4 '-dinonyl -2,2 '-bipyridyl, 4,4 '-dinonyl -2,2 '-bipyridyl and five
The combination of methyl diethylenetriamine, the combination of pentamethyl-diethylenetriamine and three (2- dimethylaminoethyl) amine or three (2- diformazans
Amino-ethyl) amine, 4,4 '-dinonyl -2,2 '-bipyridyl and the combination of pentamethyl-diethylenetriamine etc..
Preferably, the third solvent includes in dimethyl sulfoxide, toluene, tetrahydrofuran, chloroform or dimethylformamide
Any one or at least two combination, the combination is typical but non-limiting example has: the group of dimethyl sulfoxide and toluene
Close, toluene and the combination of tetrahydrofuran, the combination of tetrahydrofuran and chloroform, chloroform and dimethylformamide combination, dimethyl
The combination or dimethyl sulfoxide of formamide and dimethyl sulfoxide, the combination of toluene and tetrahydrofuran etc..
Preferably, second polymerized monomer includes n-butyl acrylate, methyl methacrylate, acrylonitrile or methyl-prop
In olefin(e) acid N-butyl any one or at least two combination, the combination is typical but non-limiting example has: acrylic acid is just
The combination of butyl ester and methyl methacrylate, the combination of methyl methacrylate and acrylonitrile, acrylonitrile and methacrylic acid are just
The combination of butyl ester, the combination of n-BMA and n-butyl acrylate or n-butyl acrylate, methyl methacrylate
With the combination of acrylonitrile etc..
Preferably, the Ligands include three (2- dimethylaminoethyl) amine, 4,4 '-dinonyl -2,2 '-bipyridyls or
In pentamethyl-diethylenetriamine any one or at least two combination, the combination is typical but non-limiting example has: three
(2- dimethylaminoethyl) amine and the combination of 4,4 '-dinonyl -2,2 '-bipyridyl, 4,4 '-dinonyl -2,2 '-bipyridyl and five
The combination of methyl diethylenetriamine, the combination of pentamethyl-diethylenetriamine and three (2- dimethylaminoethyl) amine or three (2- diformazans
Amino-ethyl) amine, 4,4 '-dinonyl -2,2 '-bipyridyl and the combination of pentamethyl-diethylenetriamine etc..
Preferably, the 4th solvent includes in dimethyl sulfoxide, toluene, tetrahydrofuran, chloroform or dimethylformamide
Any one or at least two combination, the combination is typical but non-limiting example has: the group of dimethyl sulfoxide and toluene
Close, toluene and the combination of tetrahydrofuran, the combination of tetrahydrofuran and chloroform, chloroform and dimethylformamide combination, dimethyl
The combination or dimethyl sulfoxide of formamide and dimethyl sulfoxide, the combination of toluene and tetrahydrofuran etc..
In the present invention, first initiator and the second initiator separately can be 2- bromine anthracene, 1,5- dibromo
In anthracene, 2,6- dibromoanthracene, N- (4- bromophenyl) maleimide or N- (4- chlorphenyl) maleimide any one or extremely
Few two kinds of combination, the combination is typical but non-limiting example has: 2- bromine anthracene and 1, the combination of 5- dibromoanthracene, 1,5- dibromoanthracene
The combination of combination, 2,6- dibromoanthracene and N- (4- bromophenyl) maleimide with 2,6- dibromoanthracene, N- (4- bromophenyl) Malaysia
The combination of acid imide and N- (4- chlorphenyl) maleimide or 2- bromine anthracene, 1,5- dibromoanthracene and the combination of 2,6- dibromoanthracene etc..
As currently preferred technical solution, second solvent includes dimethyl sulfoxide, toluene, tetrahydrofuran, chlorine
In imitative or dimethylformamide any one or at least two combination, the combination typical case but non-limiting example has: two
The combination of methyl sulfoxide and toluene, the combination of toluene and tetrahydrofuran, tetrahydrofuran and chloroform combination, chloroform and dimethyl methyl
The combination of amide, the combination or dimethyl sulfoxide of dimethylformamide and dimethyl sulfoxide, the combination of toluene and tetrahydrofuran etc..
As currently preferred technical solution, one fluoroacetic acid of fluoro organic acid, difluoroacetic acid, trifluoroacetic acid, three
In fluorine propionic acid, five fluorine propionic acid or perfluorobutyric acid any one or at least two combination, the group of a fluoroacetic acid and difluoroacetic acid
Close, difluoroacetic acid and the combination of trifluoroacetic acid, the combination of trifluoroacetic acid and trifluoroacetic acid, trifluoroacetic acid and five fluorine propionic acid group
Conjunction, the combination of five fluorine propionic acid and perfluorobutyric acid, the combination of perfluorobutyric acid and trifluoroacetic acid or trifluoroacetic acid, five fluorine propionic acid and perfluor
The combination etc. of butyric acid.
Preferably, first solvent includes in dimethyl sulfoxide, toluene, tetrahydrofuran, chloroform or dimethylformamide
Any one or at least two combination, the combination is typical but non-limiting example has: the group of dimethyl sulfoxide and toluene
Close, toluene and the combination of tetrahydrofuran, the combination of tetrahydrofuran and chloroform, chloroform and dimethylformamide combination, dimethyl
The combination or dimethyl sulfoxide of formamide and dimethyl sulfoxide, the combination of toluene and tetrahydrofuran etc..
In the present invention, the functional groups in the silicon-based anode binder can form chemical bond with the group on the surface Si
It closes；Adhesive modulus in the present invention is larger, and elasticity preferably, can effectively be sustained silicium cathode and expand generated stress；This hair
Binder component in bright can form supermolecule crosslinked action with Si surface group, and the expansion in cyclic process can be effectively suppressed.
The second purpose of the present invention is to provide a kind of preparation method of above-mentioned silicon-based anode binder, the preparation method packets
Include following steps:
First polymerized monomer, the first complexing agent, stannous chloride, the first initiator and third solvent are mixed, body is removed
After oxygen and water in system, is reacted under protective atmosphere, obtain first polymer after reaction；
Second polymerized monomer, the second complexing agent, copper chloride, the second initiator and the 4th solvent are mixed, system is removed
In oxygen and water after, be added copper powder, reacted under protective atmosphere, obtain second polymer after reaction；
The first polymer and the second polymer are mixed with the second solvent, and reaction is heated under protective atmosphere,
Block copolymer is obtained after reaction；
The block copolymer is mixed with the first solvent and fluoroacetic, obtains the silicon-based anode after reaction
Binder.
As currently preferred technical solution, the method for oxygen and water is Frozen-thawed cycled in the removing system.
Preferably, the number of the Frozen-thawed cycled is 1~5 time, and such as 1 time, 2 times, 3 times, 4 times or 5 are inferior, but simultaneously not only limit
It is equally applicable in other unlisted numerical value in cited numerical value, each numberical range.
Preferably, prepare the first polymer reaction temperature be 15~35 DEG C, such as 15 DEG C, 16 DEG C, 18 DEG C, 20 DEG C,
22 DEG C, 25 DEG C, 28 DEG C, 30 DEG C, 32 DEG C or 35 DEG C etc., it is not limited to cited numerical value, in each numberical range other
Unlisted numerical value is equally applicable.
Preferably, prepare the first polymer reaction time be 8~10h, as 8h, 8.2h, 8.5h, 8.8h, 9h,
9.2h, 9.5h, 9.8h or 10h etc., it is not limited to cited numerical value, other interior unlisted numerical value of each numberical range
It is equally applicable.
Preferably, prepare the second polymer reaction temperature be 15~35 DEG C, such as 15 DEG C, 16 DEG C, 18 DEG C, 20 DEG C,
22 DEG C, 25 DEG C, 28 DEG C, 30 DEG C, 32 DEG C or 35 DEG C etc., it is not limited to cited numerical value, in each numberical range other
Unlisted numerical value is equally applicable.
Preferably, the reaction time for preparing the second polymer is 7~10h, such as 7h, 7.5h, 8h, 8.5h, 9h, 9.5h
Or 10h etc., it is not limited to cited numerical value, other interior unlisted numerical value of each numberical range are equally applicable.
Preferably, prepare the block copolymer reaction temperature be 100~200 DEG C, such as 100 DEG C, 110 DEG C, 120 DEG C,
130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C or 200 DEG C etc., it is not limited to cited numerical value,
Other unlisted numerical value are equally applicable in each numberical range.
Preferably, the reaction time for preparing the block copolymer is 36~60h, such as 36h, 42h, 48h, 54h or 60h
Deng it is not limited to cited numerical value, other unlisted numerical value are equally applicable in each numberical range.
Preferably, the reaction temperature for preparing the block copolymer and fluoro organic acid is 15~35 DEG C, such as 15 DEG C, 16
DEG C, 18 DEG C, 20 DEG C, 22 DEG C, 25 DEG C, 28 DEG C, 30 DEG C, 32 DEG C or 35 DEG C etc., it is not limited to cited numerical value, each number
It is equally applicable to be worth other unlisted numerical value in range.
Preferably, the reaction time for preparing the block copolymer and fluoro organic acid is 40~50h, as 40h, 41h,
42h, 43h, 44h, 45h, 46h, 47h, 48h, 49h or 50h etc., it is not limited to cited numerical value, each numberical range
Other interior unlisted numerical value are equally applicable.
Preferably, the protective atmosphere be nitrogen, helium or argon gas in any one or at least two combination, it is described
Combination is typical but non-limiting example has: the combination of nitrogen and helium, the combination of helium and argon gas, the combination of argon gas and nitrogen or
Nitrogen, argon gas and combination of helium etc..
As currently preferred technical solution, above-mentioned silicon-based anode binder the preparation method comprises the following steps:
By 7~10 parts of the first polymerized monomer, 1~4 part of the first complexing agent, 1~3 part of stannous chloride, the first initiator 0.05
~0.1 part and 7~10 parts of third solvent mixes, after the oxygen and water in 1~5 removing system of Frozen-thawed cycled, in protection gas
15~35 DEG C of 8~10h of reaction, obtain first polymer after reaction under atmosphere；
By 6~10 parts of the second polymerized monomer, 2~5 parts of the second complexing agent, 1~3 part of copper chloride, the second initiator 0.05~
0.2 part and 6~10 parts of the 4th solvent mixes, and after the oxygen and water in 1~5 removing system of Frozen-thawed cycled, copper powder is added
0.05~0.4 part, 15~35 DEG C of 7~10h of reaction, obtain second polymer after reaction under protective atmosphere；
5~9 parts of the first polymer and 5~10 parts of the second polymer are mixed for 8~10 parts with the second solvent,
100~200 DEG C of 36~60h of reaction, obtain block copolymer after reaction under protective atmosphere；
4~10 parts of the block copolymer, 4~10 parts of fluoro organic acid and 30~50 parts of the first solvent are mixed, 15
The silicon-based anode binder is obtained after~35 DEG C of 40~50h of reaction.
Compared with prior art, the present invention at least has the advantages that
(1) present invention provides a kind of silicon-based anode binder, and the binder can be synthesized precisely, soluble easily in water, can be effective
Inhibit silicon-based anode expansion, promotes the long circulating performance of silicon-based anode；
(2) present invention provides a kind of preparation method of silicon-based anode binder, and the preparation method synthetic method is simple, work
Skill is easy, is suitable for industrialized production.
Specific embodiment
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is only to aid in the understanding present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
The present embodiment provides a kind of preparation methods of silicon-based anode binder, and the preparation method comprises the following steps:
By 7 parts of Tert-butyl Methacrylate, three 1 part of (2- dimethylaminoethyl) amine, 1 part of stannous chloride, the first initiator
0.05 part and 7 parts of dimethyl sulfoxide mixing, after the oxygen and water in 3 removing systems of Frozen-thawed cycled, in a nitrogen atmosphere 15
DEG C reaction 10h, obtain first polymer after reaction；
By 6 parts of n-butyl acrylate, three 2 parts of (2- dimethylaminoethyl) amine, 1 part of copper chloride, 0.05 part of the second initiator
And 6 parts of dimethyl sulfoxide mixing, after the oxygen and water in 3 removing systems of Frozen-thawed cycled, it is added 0.05 part of copper powder, in nitrogen
The lower 15 DEG C of reactions 10h of atmosphere, obtains second polymer after reaction；
5 parts of the first polymer and 10 parts of the second polymer are mixed with 8 parts of tetrahydrofuran, in nitrogen atmosphere
Lower 100 DEG C of reactions 60h, obtains block copolymer after reaction；
4 parts of the block copolymer, 4 parts of difluoroacetic acid and 30 parts of methylene chloride are mixed, are obtained after 15 DEG C of reaction 50h
The silicon-based anode binder.
Embodiment 2
The present embodiment provides a kind of preparation methods of silicon-based anode binder, and the preparation method comprises the following steps:
By 10 parts of acrylonitrile, 4 parts of 4,4 '-dinonyl -2,2 '-bipyridyl, 3 parts of stannous chloride, 0.1 part of the first initiator with
And 10 parts of tetrahydrofuran mixing, after the oxygen and water in 5 removing systems of Frozen-thawed cycled, 35 DEG C of reaction 8h under helium atmosphere,
First polymer is obtained after reaction；
By 10 parts of methyl methacrylate, 5 parts of 4,4 '-dinonyl -2,2 '-bipyridyl, 3 parts of copper chloride, the second initiator
0.2 part and 10 parts of tetrahydrofuran mixes, and after the oxygen and water in 5 removing systems of Frozen-thawed cycled, is added 0.4 part of copper powder,
The lower 35 DEG C of reactions 10h of helium atmosphere, obtains second polymer after reaction；
9 parts of the first polymer and 5 parts of the second polymer are mixed with 10 parts of tetrahydrofuran, in helium atmosphere
Lower 200 DEG C of reactions 36h, obtains block copolymer after reaction；
10 parts of the block copolymer, 10 parts of perfluorobutyric acid and 50 parts of tetrahydrofuran are mixed, after 35 DEG C of reaction 40h
To the silicon-based anode binder.
Embodiment 3
The present embodiment provides a kind of preparation methods of silicon-based anode binder, and the preparation method comprises the following steps:
By 8 parts of methyl methacrylate, 2 parts of pentamethyl-diethylenetriamine, 1.5 parts of stannous chloride, the first initiator 0.08
Part and 8 parts of chloroform mixing, after the oxygen and water in 3 removing systems of Frozen-thawed cycled, 20 DEG C of reaction 9h in a nitrogen atmosphere, instead
First polymer is obtained after answering；
By 8 parts of n-BMA, 3 parts of pentamethyl-diethylenetriamine, 1.8 parts of copper chloride, 0.1 part of the second initiator
And 8 parts of chloroform mixing, after the oxygen and water in 3 removing systems of Frozen-thawed cycled, it is added 0.1 part of copper powder, in a nitrogen atmosphere
20 DEG C of reaction 9h, obtain second polymer after reaction；
6 parts of the first polymer and 8 parts of the second polymer are mixed with 8.5 parts of chloroform, in a nitrogen atmosphere
150 DEG C of reaction 42h, obtain block copolymer after reaction；
5 parts of the block copolymer, 5 parts of five fluorine propionic acid and 37 parts of chloroform are mixed, are obtained after 20 DEG C of reaction 42h described
Silicon-based anode binder.
Embodiment 4
The present embodiment provides a kind of preparation methods of silicon-based anode binder, and the preparation method comprises the following steps:
By 9 parts of tert-butyl acrylate, three 3 parts of (2- dimethylaminoethyl) amine, 2.5 parts of stannous chloride, the first initiator
0.08 part and DMF 9 parts mix, after the oxygen and water in 3 removing systems of Frozen-thawed cycled, 25 DEG C of reactions in a nitrogen atmosphere
8h obtains first polymer after reaction；
By 9 parts of acrylonitrile, 4 parts of 4,4 '-dinonyl -2,2 '-bipyridyl, 2.5 parts of copper chloride, 0.15 part of the second initiator with
9 parts of DMF mix, and after the oxygen and water in 3 removing systems of Frozen-thawed cycled, are added 0.3 part of copper powder, in a nitrogen atmosphere 25 DEG C
8h is reacted, obtains second polymer after reaction；
8 parts of the first polymer and 8 parts of the second polymer are mixed with 9 parts of DMF, in a nitrogen atmosphere 120
DEG C reaction 48h, obtain block copolymer after reaction；
8 parts of the block copolymer, 6 parts of trifluoroacetic acid and 45 parts of DMF are mixed, are obtained after 25 DEG C of reaction 48h described
Silicon-based anode binder.
Embodiment 5
The present embodiment provides a kind of preparation methods of silicon-based anode binder, and the preparation method comprises the following steps:
8 parts of n-isopropyl acrylamide, 2 parts of 4,4 '-dinonyl -2,2 '-bipyridyl, 2 parts of stannous chloride, first are caused
0.08 part of agent and 9 parts of toluene mixing, after the oxygen and water in 3 removing systems of Frozen-thawed cycled, in a nitrogen atmosphere 25 DEG C it is anti-
10h is answered, obtains first polymer after reaction；
By 8 parts of methyl methacrylate, three 3 parts of (2- dimethylaminoethyl) amine, 2 parts of copper chloride, 0.1 part of the second initiator
And 8 parts of toluene mixing, after the oxygen and water in 3 removing systems of Frozen-thawed cycled, it is added 0.2 part of copper powder, in a nitrogen atmosphere
25 DEG C of reaction 8h, obtain second polymer after reaction；
8 parts of the first polymer and 7 parts of the second polymer are mixed with 9 parts of toluene, 120 under protective atmosphere
DEG C reaction 48h, obtain block copolymer after reaction；
8 parts of the block copolymer, 6 parts of trifluoroacetic acid and 35 parts of chloroform are mixed, are obtained after 25 DEG C of reaction 48h described
Silicon-based anode binder.
Comparative example 1
Using the first polymer that comparative example 3 is prepared as binder.
Comparative example 2
Using the second polymer that comparative example 3 is prepared as binder.
Embodiment 1-5 and comparative example 1-2 the silicon-based anode binder provided are used to prepare silicon-based anode pole piece, and group
Battery is dressed up, the cycle performance of expansion rate and battery to silicon-based anode pole piece is tested, and the results are shown in Table 1.
Expansion rate test method is as follows: using pole piece thickness after miking roll-in, being averaged postscript is a1；Afflux
Body thickness is defined as a0；After circulating battery, battery is disassembled, using miking negative electrode tab thickness, being averaged postscript is a2,
Then negative electrode tab expansion rate x%=(a2-a1)/(a1-a0) × 100%.
Cycle performance of battery test method:
Charging: 1C multiplying power constant-current charge to 4.2V, then constant-voltage charge to electric current is down to 0.05C；
Electric discharge: 1C multiplying power discharging to 2.75V.
Table 1
| Cathode pole piece expansion rate/% | Cycle performance | |
| Embodiment 1 | 35 | 670 |
| Embodiment 2 | 30 | 790 |
| Embodiment 3 | 25 | 960 |
| Embodiment 4 | 22 | 1200 |
| Embodiment 5 | 24 | 1100 |
| Comparative example 1 | 48 | 340 |
| Comparative example 2 | 50 | 320 |
From the results shown in Table 1, it is negative that the silicon-based anode binder that 1-5 of the embodiment of the present invention is provided is used to prepare silicon substrate
Pole pole piece, and it is assembled into battery, for cathode pole piece after circulation 1200 times, expansion rate can be down to 22%.And comparative example 1 is with reality
First polymer that example 3 is prepared is applied as binder, the battery that the silicon-based anode pole piece being prepared is prepared is (out
Outside cathode pole piece, the other assemblies of battery are same as Example 3) circulation 340 times when, the expansion rate of cathode pole piece just reaches
48%.Likewise, comparative example 2 closes object as binder using embodiment 3 is prepared second, the silicon-based anode being prepared
When the battery (out outside cathode pole piece, the other assemblies of battery are same as Example 3) that pole piece is prepared recycles 320 times, bear
The expansion rate of pole pole piece has just reached 50%, and effect is much worse than embodiment 3.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (10)
1. a kind of silicon-based anode binder, which is characterized in that the binder is the amphipathic block organic acid modified by fluoro
Copolymer.
2. binder according to claim 1, which is characterized in that the raw material of the binder includes: in parts by weight
4~10 parts of block copolymer, 30~50 parts of 4~10 parts of fluoro organic acid and the first solvent.
3. binder according to claim 1 or 2, which is characterized in that synthesize the block copolymer in parts by weight
Raw material include: 5~9 parts of first polymer, 8~10 parts of 5~10 parts of second polymer and the second solvent.
4. binder according to claim 1-3, which is characterized in that it is poly- to synthesize described first in parts by weight
The raw material for closing object includes: 7~10 parts of the first polymerized monomer, the first 1~4 part of complexing agent, and 1~3 part of stannous chloride, the first initiator
0.05~0.1 part and 7~10 parts of third solvent；
Preferably, the raw material for synthesizing the second polymer in parts by weight includes: 6~10 parts of the second polymerized monomer, and second
2~5 parts of complexing agent, 1~3 part of copper chloride, 0.05~0.4 part of copper powder, the second 0.05~0.2 part of initiator and the 4th solvent 6
~10 parts.
5. binder according to claim 4, which is characterized in that first polymerized monomer includes the tertiary fourth of methacrylic acid
Any one in ester, acrylonitrile, methyl methacrylate, tert-butyl acrylate or n-isopropyl acrylamide or at least two
Combination；
Preferably, first ligand includes three (2- dimethylaminoethyl) amine, 4,4 '-dinonyl -2,2 '-bipyridyls or five first
In base diethylenetriamine any one or at least two combination；
Preferably, the third solvent includes appointing in dimethyl sulfoxide, toluene, tetrahydrofuran, chloroform or dimethylformamide
It anticipates a kind of or at least two combinations；
Preferably, second polymerized monomer includes n-butyl acrylate, methyl methacrylate, acrylonitrile or methacrylic acid
In N-butyl any one or at least two combination；
Preferably, the Ligands include three (2- dimethylaminoethyl) amine, 4,4 '-dinonyl -2,2 '-bipyridyls or five first
In base diethylenetriamine any one or at least two combination；
Preferably, the 4th solvent includes appointing in dimethyl sulfoxide, toluene, tetrahydrofuran, chloroform or dimethylformamide
It anticipates a kind of or at least two combinations.
6. binder according to claim 1-5, which is characterized in that second solvent includes dimethyl Asia
In sulfone, toluene, tetrahydrofuran, chloroform or dimethylformamide any one or at least two combination.
7. binder according to claim 1-6, which is characterized in that one fluoroacetic acid of fluoro organic acid, two
In fluoroacetic acid, trifluoroacetic acid, trifluoroacetic acid, five fluorine propionic acid or perfluorobutyric acid any one or at least two combination；
Preferably, first solvent includes appointing in dimethyl sulfoxide, toluene, tetrahydrofuran, chloroform or dimethylformamide
It anticipates a kind of or at least two combinations.
8. a kind of preparation method of the described in any item binders of claim 1-7, which is characterized in that the preparation method includes
Following steps:
First polymerized monomer, the first complexing agent, stannous chloride, the first initiator and third solvent are mixed, in removing system
Oxygen and water after, reacted under protective atmosphere, obtain first polymer after reaction；
Second polymerized monomer, the second complexing agent, copper chloride, the second initiator and the 4th solvent are mixed, in removing system
After oxygen and water, copper powder is added, is reacted under protective atmosphere, obtains second polymer after reaction；
The first polymer and the second polymer are mixed with the second solvent, and reaction, reaction are heated under protective atmosphere
After obtain block copolymer；
The block copolymer is mixed with the first solvent and fluoroacetic, obtains the silicon-based anode bonding after reaction
Agent.
9. preparation method according to claim 8, which is characterized in that the method for oxygen and water is to freeze in the removing system
Melt circulation；
Preferably, the number of the Frozen-thawed cycled is 1~5 time；
Preferably, the reaction temperature for preparing the first polymer is 15~35 DEG C；
Preferably, the reaction time for preparing the first polymer is 8~10h；
Preferably, the reaction temperature for preparing the second polymer is 15~35 DEG C；
Preferably, the reaction time for preparing the second polymer is 7~10h；
Preferably, the reaction temperature for preparing the block copolymer is 100~200 DEG C；
Preferably, the reaction time for preparing the block copolymer is 36~60h；
Preferably, the reaction temperature for preparing the block copolymer and fluoro organic acid is 15~35 DEG C；
Preferably, the reaction time for preparing the block copolymer and fluoro organic acid is 40~50h；
Preferably, the protective atmosphere be nitrogen, helium or argon gas in any one or at least two combination.
10. preparation method according to claim 8 or claim 9, which is characterized in that the preparation method comprises the following steps:
By 7~10 parts of the first polymerized monomer, 1~4 part of the first complexing agent, 1~3 part of stannous chloride, the first initiator 0.05~0.1
Part and 7~10 parts of third solvent mixing, after the oxygen and water in 1~5 removing system of Frozen-thawed cycled, 15 under protective atmosphere
~35 DEG C of 8~10h of reaction, obtain first polymer after reaction；
By 6~10 parts of the second polymerized monomer, 2~5 parts of the second complexing agent, 1~3 part of copper chloride, 0.05~0.2 part of the second initiator
And 6~10 parts of the 4th solvent mixing, after the oxygen and water in 1~5 removing system of Frozen-thawed cycled, be added copper powder 0.05~
0.4 part, 15~35 DEG C of 7~10h of reaction, obtain second polymer after reaction under protective atmosphere；
5~9 parts of the first polymer and 5~10 parts of the second polymer are mixed for 8~10 parts with the second solvent, protected
100~200 DEG C of 36~60h of reaction under atmosphere are protected, obtain block copolymer after reaction；
4~10 parts of the block copolymer, 4~10 parts of fluoro organic acid and 30~50 parts of the first solvent are mixed, 15~35
DEG C reaction 40~50h after obtain the silicon-based anode binder.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110797538A (en) * | 2019-11-07 | 2020-02-14 | 惠州亿纬锂能股份有限公司 | Silicon-based negative electrode binder, preparation method thereof and application thereof in lithium ion battery |
| CN111430667A (en) * | 2019-12-31 | 2020-07-17 | 蜂巢能源科技有限公司 | Negative electrode slurry, negative electrode plate, power battery and electric automobile |
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| CN107611344A (en) * | 2017-09-17 | 2018-01-19 | 亚士创能科技(上海)股份有限公司 | The dual cross-linked binder of lithium battery silicon based anode material, lithium battery silicon based anode material and preparation method, GND and lithium battery |
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| CN107611344A (en) * | 2017-09-17 | 2018-01-19 | 亚士创能科技(上海)股份有限公司 | The dual cross-linked binder of lithium battery silicon based anode material, lithium battery silicon based anode material and preparation method, GND and lithium battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110797538A (en) * | 2019-11-07 | 2020-02-14 | 惠州亿纬锂能股份有限公司 | Silicon-based negative electrode binder, preparation method thereof and application thereof in lithium ion battery |
| CN111430667A (en) * | 2019-12-31 | 2020-07-17 | 蜂巢能源科技有限公司 | Negative electrode slurry, negative electrode plate, power battery and electric automobile |
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