CN112687854A - Silicon monoxide composite negative electrode material of lithium ion battery and preparation method and application thereof - Google Patents
Silicon monoxide composite negative electrode material of lithium ion battery and preparation method and application thereof Download PDFInfo
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- 239000007773 negative electrode material Substances 0.000 title claims abstract description 101
- 239000002131 composite material Substances 0.000 title claims abstract description 86
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 title abstract description 122
- 238000003756 stirring Methods 0.000 claims abstract description 62
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 58
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000004814 polyurethane Substances 0.000 claims abstract description 54
- 229920002635 polyurethane Polymers 0.000 claims abstract description 54
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 50
- 239000002994 raw material Substances 0.000 claims abstract description 33
- 239000002356 single layer Substances 0.000 claims abstract description 27
- 239000012790 adhesive layer Substances 0.000 claims abstract description 24
- 238000001914 filtration Methods 0.000 claims abstract description 18
- 239000000853 adhesive Substances 0.000 claims abstract description 14
- 230000001070 adhesive effect Effects 0.000 claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 51
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 18
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002202 Polyethylene glycol Substances 0.000 claims description 17
- 229920001223 polyethylene glycol Polymers 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 11
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims 2
- 239000010410 layer Substances 0.000 abstract description 50
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 18
- 239000010703 silicon Substances 0.000 abstract description 18
- 229910052710 silicon Inorganic materials 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 6
- 239000010405 anode material Substances 0.000 abstract 2
- 229920002125 Sokalan® Polymers 0.000 description 24
- 239000004584 polyacrylic acid Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 22
- 239000010406 cathode material Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- -1 and specifically Substances 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to the technical field of preparation of lithium ion battery anode materials, and discloses a lithium ion battery silicon oxide composite anode material and a preparation method and application thereof, wherein the preparation method comprises the following steps: providing an adhesive, adding the adhesive into dimethylformamide, and uniformly stirring to obtain a first adhesive layer solution; providing a silicon monoxide raw material, adding the silicon monoxide raw material into the first bonding layer solution, uniformly stirring, and filtering to obtain a silicon monoxide single-layer composite negative electrode material; providing modified polyurethane, adding the monofilm composite negative electrode material of the silicon oxide into the modified polyurethane, uniformly stirring, and filtering to obtain the monofilm composite negative electrode material of the lithium ion battery. The double-layer structure is formed on the surface of the silicon oxide material, so that the gradual dissipation of the stress of the silicon oxide composite negative electrode material of the lithium ion battery is realized, the quick self-repairing function is realized, the problem of large volume expansion of the silicon negative electrode material can be effectively solved, and the circulation stability of the silicon negative electrode material is remarkably improved.
Description
Technical Field
The invention relates to the technical field of preparation of lithium ion battery cathode materials, in particular to a silicon monoxide composite cathode material of a lithium ion battery and a preparation method and application thereof.
Background
In recent years, lithium ion batteries are widely applied to portable electronic products such as mobile phones, tablet computers, notebook computers, digital cameras and the like, and are one of the most potential energy storage devices, which bring convenience to the lives of people, but with the improvement of living standards of people, the performance requirements on the lithium ion batteries are higher and higher, at present, the traditional lithium ion batteries are difficult to meet the continuously increasing requirements of high-power electric vehicles and other large-scale energy storage fields, which promotes the extensive research on novel negative electrode materials capable of providing high energy density, and in the negative electrode materials, silicon negative electrode materials are considered as negative electrode materials capable of effectively improving the energy density of the lithium ion batteries due to the fact that the silicon negative electrode materials have high theoretical specific capacity of 4200mAh/g, and are widely concerned and researched.
However, the silicon negative electrode material has huge volume change and unstable structure in the charge and discharge cycle process, and can cause serious pulverization of silicon particles and formation of unstable SEI film, which can affect the performance of the prepared lithium ion battery, for example, seriously affect the service life of the battery, thus seriously hindering the practical application of the silicon monoxide negative electrode material, and therefore, the improvement of the structural stability and the cyclic expansion of the silicon negative electrode material is a key and difficult point of the current research on the silicon negative electrode material.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides the preparation method and the application of the lithium ion battery silicon monoxide composite negative electrode material, which can effectively solve the problem of large volume expansion of the silicon negative electrode and remarkably improve the structural stability and the cycling stability of the silicon negative electrode.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a silicon monoxide composite negative electrode material of a lithium ion battery comprises the following steps:
providing an adhesive, adding the adhesive into dimethylformamide, and uniformly stirring to obtain a first adhesive layer solution;
providing a silicon monoxide raw material, adding the silicon monoxide raw material into the first bonding layer solution, uniformly stirring, and filtering to obtain a silicon monoxide single-layer composite negative electrode material;
providing modified polyurethane, adding the silicon monoxide single-layer composite negative electrode material into the modified polyurethane, uniformly stirring, and filtering to obtain the silicon monoxide composite negative electrode material of the lithium ion battery.
In one embodiment, the binder is polyacrylic acid.
In one embodiment, in the operation of providing the modified polyurethane, isophorone diisocyanate and polyethylene glycol are added into dimethylformamide, stirred uniformly, then a catalyst is added, a first polymerization reaction is carried out to obtain a polymer A, 4' -dicarboxydiphenyl disulfide is added into the polymer A, and a second polymerization reaction is carried out to obtain the modified polyurethane.
In one embodiment, the catalyst is dibutyltin dilaurate.
In one embodiment, the first polymerization is carried out for 12 to 24 hours at a first polymerization temperature of 25 to 35 ℃.
In one embodiment, the second polymerization reaction is carried out in an operation in which the second polymerization time is controlled to be 12 to 24 hours and the second polymerization temperature is controlled to be 25 to 35 ℃.
In one embodiment, the stirring time is controlled to be 5 to 10 hours in the operation of adding the raw material of the silicon monoxide to the first adhesive layer solution and uniformly stirring.
In one embodiment, in the operation of adding the silicon monoxide single-layer composite negative electrode material into the modified polyurethane and uniformly stirring, the stirring time is controlled to be 5-10 h.
In one embodiment, the mass ratio of the isophorone diisocyanate, the 4,4' -dicarboxydiphenyl disulfide and the polyethylene glycol is 1-2: 1-2: 20.
a silicon monoxide composite negative electrode material of a lithium ion battery is prepared by the preparation method of the silicon monoxide composite negative electrode material of the lithium ion battery. The lithium ion battery cathode material has good application prospect in lithium battery cathode materials.
Compared with the prior art, the invention has at least the following advantages:
(1) according to the invention, the silicon oxide raw material is added into the first bonding layer solution, the mixture is stirred uniformly to react, then the first bonding layer is formed on the surface of the silicon oxide raw material, the silicon oxide single-layer composite negative electrode material is obtained, then the modified polyurethane is provided, the silicon oxide single-layer composite negative electrode material is added into the modified polyurethane, the mixture is stirred uniformly, and the modified polyurethane layer, namely the second bonding layer, is formed on the surface of the silicon oxide single-layer composite negative electrode material, so that a double-layer structure is formed on the surface of the silicon oxide material, the lithium ion battery silicon oxide composite negative electrode material is obtained, the gradual dissipation of the stress of the lithium ion battery silicon oxide composite negative electrode material can be realized, the quick self-repairing function is realized, the problem of large volume expansion of the silicon negative electrode material can be effectively solved, and the cycle stability of.
(2) The lithium ion battery silicon monoxide composite negative electrode material provided by the invention has a double-layer structure, internal stress generated in a lithium embedding process can be eliminated, and the modified polyurethane can be used as a buffer layer to disperse residual stress, so that the first bonding layer is prevented from being damaged. In addition, modified polyurethane with a quick self-repairing function is introduced to form a modified polyurethane layer, and microcracks generated by large stress can be dynamically recovered, so that the integrity and structural stability of the silicon oxide composite negative electrode material of the lithium ion battery are further ensured.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a flow chart illustrating the steps of a method for preparing a composite negative electrode material of silicon monoxide for a lithium ion battery according to an embodiment of the present invention;
fig. 2 is a comparative graph of discharge cycle performance tests of the lithium ion batteries of example 4, comparative example 1 and comparative example 2 of the present invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In one embodiment, referring to fig. 1, a method for preparing a negative silicon oxide composite material for a lithium ion battery includes the following steps:
s110, providing an adhesive, adding the adhesive into dimethylformamide, and uniformly stirring to obtain a first adhesive layer solution.
The adhesive is added into the dimethylformamide and uniformly stirred, so that a first adhesive layer solution is prepared, the subsequent silicon monoxide raw material is conveniently and better dispersed in the first adhesive layer solution, the first adhesive layer is favorably formed on the surface of the silicon monoxide raw material, and the quality of the prepared silicon monoxide composite negative electrode material of the lithium ion battery is favorably improved. In particular, the binder is polyacrylic acid. Polyacrylic acid is used as a raw material of the first bonding layer, the polyacrylic acid is a rigid bonding agent and has high Young modulus, the rigid polyacrylic acid can serve as a protective layer of the silicon protoxide material, internal stress generated in a lithium embedding process can be eliminated, and the silicon protoxide material can be well protected, so that structural stability and integrity of the prepared silicon protoxide composite negative electrode material of the lithium ion battery are ensured.
S120, providing a silicon monoxide raw material, adding the silicon monoxide raw material into the first bonding layer solution, uniformly stirring, and filtering to obtain the silicon monoxide single-layer composite negative electrode material.
The first binding agent layer is formed on the surface of the silica raw material, that is, the polyacrylic acid binding agent layer is formed, and can be used as a protective layer of the silica material, so that the structural stability and integrity of the prepared silica composite negative electrode material of the lithium ion battery are ensured.
In one embodiment, in the operation of adding the raw material of the silica to the solution of the first adhesive layer and uniformly stirring, the stirring time is controlled to be 5 to 10 hours. It should be noted that, when the raw material of the silicon monoxide reacts in the solution of the first adhesive layer to form the first adhesive layer, the integrity of the first adhesive layer and the layer formation needs to be ensured, the formation of the first adhesive layer with a complete structure is favorably ensured by increasing the reaction time, when the stirring time is less than 5 hours, the reaction time is too short, the structural integrity of the formed first adhesive layer cannot be ensured, the quality of the subsequently prepared silicon monoxide composite negative electrode material of the lithium ion battery is easily influenced, when the stirring time is more than 10 hours, the reaction time is too long, the time cost is greatly increased, and the production benefit is not favorably improved, so that the stirring time is controlled to be 5 hours to 10 hours, and thus, the first adhesive layer with a complete structure and moderate thickness, namely the polyacrylic acid adhesive layer, can be formed on the surface of the raw material of the silicon monoxide.
S130, providing modified polyurethane, adding the silicon monoxide single-layer composite negative electrode material into the modified polyurethane, uniformly stirring, and filtering to obtain the silicon monoxide composite negative electrode material of the lithium ion battery.
It is to be noted that, the monox composite negative electrode material is added into the modified polyurethane, and is uniformly stirred and reacts to form a second adhesive layer on the surface of the monox composite negative electrode material, that is, a modified polyurethane adhesive layer is formed, the modified polyurethane is a flexible adhesive, has a low young modulus, and serves as an outer layer structure, and can serve as a buffer layer to disperse residual stress, so as to avoid the rigid polyacrylic acid layer from being damaged, therefore, the inner layer of the prepared monox composite negative electrode material for the lithium ion battery is polyacrylic acid with a high young modulus, that is, a rigid inner layer structure, and the outer layer is the modified polyurethane with a low young modulus, so that the monox composite negative electrode material for the lithium ion battery has a structure with gradient distribution from hard to soft, and the rigid polyacrylic acid serves as a protective layer, and can eliminate internal stress generated in the lithium embedding process of the monox composite negative electrode material for the lithium ion battery, the modified polyurethane can disperse residual stress as a buffer layer, so that a rigid polyacrylic acid layer is prevented from being damaged, meanwhile, the introduced modified polyurethane has a quick self-repairing function, and microcracks generated under high stress can be dynamically recovered, so that the structural stability and integrity of the silicon oxide composite negative electrode material of the lithium ion battery are further ensured, the problem of large-volume expansion of the silicon negative electrode material can be effectively solved, and the cycle stability of the silicon negative electrode material is remarkably improved.
In one embodiment, in the operation of providing the modified polyurethane, isophorone diisocyanate and polyethylene glycol are added into dimethylformamide, stirred uniformly, then a catalyst is added, a first polymerization reaction is carried out to obtain a polymer A, and 4,4' -dicarboxydiphenyl disulfide is added into the polymer A, a second polymerization reaction is carried out to obtain the modified polyurethane. It is understood that isophorone diisocyanate is abbreviated as IPDI and has the formula C12H18N2O2The polymer A is prepared by reacting alicyclic diisocyanate with polyethylene glycol under the action of a catalyst, and specifically, the catalyst is dibutyltin dilaurate. That is, a polyurethane catalyst dibutyltin dilaurate is adopted, the specific reaction is that isophorone diisocyanate and polyethylene glycol are dissolved in dimethylformamide, a catalyst dibutyltin dilaurate is added, a first polymerization reaction is carried out, a polymer A is obtained after the reaction for a period of time, and the chemical structural formula of the polymer A is as follows:
then adding 4,4' -dicarboxydiphenyl disulfide, carrying out secondary polymerization reaction for a period of time to obtain the modified polyurethane, wherein the chemical structural formula of the modified polyurethane is as follows:
wherein n1 is more than or equal to 45 and less than or equal to 110, and n2 is more than or equal to 10 and less than or equal to 30. The prepared modified polyurethane is a flexible adhesive, has low Young modulus, can serve as a buffer layer to disperse residual stress, so that a rigid polyacrylic acid layer is prevented from being damaged, and meanwhile, the modified polyurethane has a quick self-repairing function and can dynamically recover microcracks generated under large stress, so that the structural stability and integrity of the silicon oxide composite negative electrode material of the lithium ion battery are further ensured, the problem of large-volume expansion of the silicon negative electrode material can be effectively solved, and the cycle stability of the silicon negative electrode material is remarkably improved.
In one embodiment, in the operation of carrying out the first polymerization reaction, the first polymerization time is controlled to be 12 to 24 hours, and the first polymerization temperature is controlled to be 25 to 35 ℃. In the operation of carrying out the secondary polymerization reaction, the secondary polymerization time is controlled to be 12-24 h, and the secondary polymerization temperature is controlled to be 25-35 ℃. Thus, the full progress of the polymerization reaction is ensured, and the modified polyurethane with good quality is prepared.
In one embodiment, the mass ratio of the isophorone diisocyanate to the 4,4' -dicarboxydiphenyl disulfide to the polyethylene glycol is 1-2: 1-2: 20. it can be understood that the mass ratio of isophorone diisocyanate, 4' -dicarboxydiphenyl disulfide and polyethylene glycol is strictly limited, so that the polymerization reaction of the substances according to a certain proportion can be ensured, the preparation of modified polyurethane with excellent performance can be ensured, and the subsequent preparation of the high-quality silicon oxide composite negative electrode material for the lithium ion battery can be facilitated.
In one embodiment, in the operation of adding the silicon monoxide single-layer composite negative electrode material into the modified polyurethane and uniformly stirring, the stirring time is controlled to be 5-10 h. When the single-layer composite negative electrode material of silicon oxide is reacted in the modified polyurethane to form the second binder layer, the integrity of the second adhesive and the layer formation needs to be ensured, and the formation of the second adhesive layer with complete structure is facilitated by increasing the reaction time, when the stirring time is less than 5 hours, the reaction time is too short, the structural integrity of the formed second adhesive layer cannot be ensured, the quality of the subsequently prepared silicon oxide composite negative electrode material of the lithium ion battery is easily influenced, when the stirring time is longer than 10 hours, the reaction time is too long, the time cost is greatly increased, and the production benefit is not favorably improved, so that the stirring time is preferably controlled to be 5 to 10 hours, and thus, the second adhesive layer with complete structure and moderate thickness, namely the modified polyurethane adhesive layer, can be formed on the surface of the monofilm composite negative electrode material of the monofilm silicon oxide.
A silicon monoxide composite negative electrode material of a lithium ion battery is prepared by the preparation method of the silicon monoxide composite negative electrode material of the lithium ion battery. The lithium ion battery cathode material has good application prospect in lithium battery cathode materials.
Compared with the prior art, the invention has at least the following advantages:
(1) according to the invention, the silicon oxide raw material is added into the first bonding layer solution, the mixture is stirred uniformly to react, then the first bonding layer is formed on the surface of the silicon oxide raw material, the silicon oxide single-layer composite negative electrode material is obtained, then the modified polyurethane is provided, the silicon oxide single-layer composite negative electrode material is added into the modified polyurethane, the mixture is stirred uniformly, and the modified polyurethane layer, namely the second bonding layer, is formed on the surface of the silicon oxide single-layer composite negative electrode material, so that a double-layer structure is formed on the surface of the silicon oxide material, the lithium ion battery silicon oxide composite negative electrode material is obtained, the gradual dissipation of the stress of the lithium ion battery silicon oxide composite negative electrode material can be realized, the quick self-repairing function is realized, the problem of large volume expansion of the silicon negative electrode material can be effectively solved, and the cycle stability of.
(2) The lithium ion battery silicon monoxide composite negative electrode material provided by the invention has a double-layer structure, internal stress generated in a lithium embedding process can be eliminated, and the modified polyurethane can be used as a buffer layer to disperse residual stress, so that the first bonding layer is prevented from being damaged. In addition, modified polyurethane with a quick self-repairing function is introduced to form a modified polyurethane layer, and microcracks generated by large stress can be dynamically recovered, so that the integrity and structural stability of the silicon oxide composite negative electrode material of the lithium ion battery are further ensured.
The following is a detailed description of the embodiments.
Example 1
Providing polyacrylic acid, adding the polyacrylic acid into dimethylformamide, and uniformly stirring to obtain a first bonding layer solution;
providing a silicon monoxide raw material, adding the silicon monoxide raw material into the first bonding layer solution, uniformly stirring, controlling the stirring time to be 5h, and then filtering to obtain a silicon monoxide single-layer composite negative electrode material;
adding isophorone diisocyanate and polyethylene glycol into dimethylformamide, stirring uniformly, adding dibutyltin dilaurate, carrying out primary polymerization reaction, controlling the primary polymerization time to be 12h and the primary polymerization temperature to be 25 ℃ to obtain a polymer A, adding 4,4 '-dicarboxydiphenyl disulfide into the polymer A, carrying out secondary polymerization reaction, controlling the secondary polymerization time to be 12h and the secondary polymerization temperature to be 25 ℃ to obtain the modified polyurethane, wherein the mass ratio of isophorone diisocyanate to 4,4' -dicarboxydiphenyl disulfide to polyethylene glycol is 1: 1: and 20, adding the silicon monoxide single-layer composite negative electrode material into the modified polyurethane, uniformly stirring, controlling the stirring time to be 5 hours, and then filtering to obtain the silicon monoxide composite negative electrode material of the lithium ion battery in the embodiment 1.
Example 2
Providing polyacrylic acid, adding the polyacrylic acid into dimethylformamide, and uniformly stirring to obtain a first bonding layer solution;
providing a silicon monoxide raw material, adding the silicon monoxide raw material into the first bonding layer solution, uniformly stirring, controlling the stirring time to be 8h, and then filtering to obtain a silicon monoxide single-layer composite negative electrode material;
adding isophorone diisocyanate and polyethylene glycol into dimethylformamide, stirring uniformly, adding dibutyltin dilaurate, carrying out primary polymerization reaction, controlling the primary polymerization time to be 20h and the primary polymerization temperature to be 30 ℃ to obtain a polymer A, adding 4,4 '-dicarboxydiphenyl disulfide into the polymer A, carrying out secondary polymerization reaction, controlling the secondary polymerization time to be 20h and the secondary polymerization temperature to be 30 ℃ to obtain the modified polyurethane, wherein the mass ratio of isophorone diisocyanate to 4,4' -dicarboxydiphenyl disulfide to polyethylene glycol is 1.5: 1.5: and 20, adding the silicon monoxide single-layer composite negative electrode material into the modified polyurethane, uniformly stirring, controlling the stirring time to be 8 hours, and then filtering to obtain the silicon monoxide composite negative electrode material of the lithium ion battery in the embodiment 2.
Example 3
Providing polyacrylic acid, adding the polyacrylic acid into dimethylformamide, and uniformly stirring to obtain a first bonding layer solution;
providing a silicon monoxide raw material, adding the silicon monoxide raw material into the first bonding layer solution, uniformly stirring, controlling the stirring time to be 10h, and then filtering to obtain a silicon monoxide single-layer composite negative electrode material;
adding isophorone diisocyanate and polyethylene glycol into dimethylformamide, stirring uniformly, adding dibutyltin dilaurate, carrying out a first polymerization reaction, controlling the first polymerization time to be 24 hours and the first polymerization temperature to be 35 ℃ to obtain a polymer A, adding 4,4 '-dicarboxydiphenyl disulfide into the polymer A, carrying out a second polymerization reaction, controlling the second polymerization time to be 24 hours and the second polymerization temperature to be 35 ℃ to obtain the modified polyurethane, wherein the mass ratio of isophorone diisocyanate to 4,4' -dicarboxydiphenyl disulfide to polyethylene glycol is 2: 2: and 20, adding the silicon monoxide single-layer composite negative electrode material into the modified polyurethane, uniformly stirring, controlling the stirring time to be 10 hours, and then filtering to obtain the silicon monoxide composite negative electrode material of the lithium ion battery in the embodiment 3.
Example 4
Providing polyacrylic acid, adding the polyacrylic acid into dimethylformamide, and uniformly stirring to obtain a first bonding layer solution;
providing a silicon monoxide raw material, adding the silicon monoxide raw material into the first bonding layer solution, uniformly stirring, controlling the stirring time to be 8.5h, and then filtering to obtain a silicon monoxide single-layer composite negative electrode material;
adding isophorone diisocyanate and polyethylene glycol into dimethylformamide, stirring uniformly, adding dibutyltin dilaurate, carrying out a first polymerization reaction, controlling the first polymerization time to be 20.5h and the first polymerization temperature to be 32 ℃ to obtain a polymer A, adding 4,4 '-dicarboxydiphenyl disulfide into the polymer A, carrying out a second polymerization reaction, controlling the second polymerization time to be 20.5h and the second polymerization temperature to be 32 ℃, and obtaining the modified polyurethane, wherein the mass ratio of isophorone diisocyanate to 4,4' -dicarboxydiphenyl disulfide to polyethylene glycol is 1.2: 1.8: and 20, adding the silicon monoxide single-layer composite negative electrode material into the modified polyurethane, uniformly stirring, controlling the stirring time to be 8.5h, and then filtering to obtain the silicon monoxide composite negative electrode material of the lithium ion battery in the embodiment 4.
Comparative example 1
Providing polyacrylic acid, adding the polyacrylic acid into dimethylformamide, and uniformly stirring to obtain a first bonding layer solution;
providing a silicon monoxide raw material, adding the silicon monoxide raw material into the first bonding layer solution, uniformly stirring, controlling the stirring time to be 8.5h, and then filtering to obtain the silicon monoxide single-layer composite negative electrode material of the lithium ion battery of the comparative example 1;
comparative example 2
Providing polyacrylic acid, adding the polyacrylic acid into dimethylformamide, and uniformly stirring to obtain a first bonding layer solution;
providing a silicon monoxide raw material, adding the silicon monoxide raw material into the first bonding layer solution, uniformly stirring, controlling the stirring time to be 8.5h, and then filtering to obtain a silicon monoxide single-layer composite negative electrode material;
and adding the monofilm composite negative electrode material of the silicon oxide into the polyurethane adhesive with the CAS number of CAS 51852-81-4 by adopting the polyurethane adhesive with the CAS number of CAS 51852-81-4, uniformly stirring, controlling the stirring time to be 8.5h, and filtering to obtain the monofilm composite negative electrode material of the lithium ion battery of the comparative example 2.
Experiment: the lithium ion battery silicon oxide composite negative electrode materials obtained in the embodiments 1 to 4 and the comparative examples 1 and 2 are used for preparing electrodes and assembling to obtain the lithium ion battery,
and (3) testing: in the above examples, the lithium ion batteries of examples 1, 2, 3 and 4 and comparative examples 1 and 2 were subjected to various tests, and the test results are shown in table 1 and fig. 2.
TABLE 1
As can be seen from the above table, compared with the lithium ion batteries of comparative example 1 and comparative example 2, the lithium ion batteries prepared in examples 1 to 4 all have excellent cycle life, the structure of the lithium ion battery is more stable, the service life is longer, the quality of the lithium ion batteries prepared in examples 1 to 4 is higher than that of comparative example 1 and comparative example 2, the preparation processes of the above embodiments are simple, the assembled lithium ion batteries show good cycle stability, and the cycle life of the lithium ion batteries is prolonged.
And (4) at normal temperature, carrying out 2C rate charging, 1C rate discharging and lithium ion battery discharging cycle performance testing. The test results show that the lithium ion batteries of the embodiments of the invention have excellent charging and discharging performance at different multiplying factors compared with the comparative examples 1 and 2, and are shown in detail in fig. 2, wherein, in order to avoid the data in the figure being too dense and difficult to distinguish, fig. 2 only takes the data of the embodiment 4 and makes a chart with the data of the comparative examples 1 and 2, and the results are shown in fig. 2. The effects of the other embodiments are similar to those of embodiment 3, and are not described again.
Specifically, fig. 2 is a comparative graph of discharge cycle performance tests of the lithium ion batteries of example 4, comparative example 1 and comparative example 2 according to the present invention. Wherein, 1 represents the lithium ion battery of example 4; 2 represents the lithium ion battery of comparative example 2; and 3 represents the lithium ion battery of comparative example 1. As can be seen from fig. 2, at room temperature, the capacity of the lithium ion battery of example 4 hardly faded and the capacity retention ratio was high, with charge at 2C rate and discharge at 1C rate, and cycling for 240 weeks. That is, the cycle performance of the lithium ion batteries of examples 1 to 4 is better than that of comparative example 1 and comparative example 2, and the results prove that the silicon oxide composite negative electrode material of the lithium ion battery prepared by the method of the invention has stable structure, good performance, long service life, excellent structural stability and cycle stability, and obviously improved cycle performance.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
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