CN119351001A - Binder for lithium ion battery and preparation method thereof - Google Patents
Binder for lithium ion battery and preparation method thereof Download PDFInfo
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- CN119351001A CN119351001A CN202411919998.5A CN202411919998A CN119351001A CN 119351001 A CN119351001 A CN 119351001A CN 202411919998 A CN202411919998 A CN 202411919998A CN 119351001 A CN119351001 A CN 119351001A
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 42
- 239000011230 binding agent Substances 0.000 title claims description 64
- 238000002360 preparation method Methods 0.000 title description 9
- 239000011247 coating layer Substances 0.000 claims abstract description 179
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 42
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 42
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 42
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 42
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 37
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 37
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 25
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229920002635 polyurethane Polymers 0.000 claims abstract description 25
- 239000004814 polyurethane Substances 0.000 claims abstract description 25
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 25
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims abstract description 22
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 16
- 239000002105 nanoparticle Substances 0.000 claims abstract description 14
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 60
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 60
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 30
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 30
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 30
- 239000005642 Oleic acid Substances 0.000 claims description 30
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 30
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 30
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 30
- 239000000843 powder Substances 0.000 claims description 24
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 16
- 239000000839 emulsion Substances 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- -1 polyoxyethylene-8-octylphenyl Polymers 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000004816 latex Substances 0.000 claims 1
- 229920000126 latex Polymers 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 abstract description 51
- 239000000853 adhesive Substances 0.000 abstract description 45
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 33
- 229910052710 silicon Inorganic materials 0.000 abstract description 33
- 239000010703 silicon Substances 0.000 abstract description 33
- 239000011856 silicon-based particle Substances 0.000 abstract description 19
- 229910052744 lithium Inorganic materials 0.000 abstract description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 12
- 230000002829 reductive effect Effects 0.000 abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 54
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 27
- 230000000694 effects Effects 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 230000005764 inhibitory process Effects 0.000 description 6
- 239000002390 adhesive tape Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 230000000670 limiting effect Effects 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- CMCZKWJUYJOKFX-IWIPYMOSSA-N (5z)-5-[[3-(1-hydroxypentyl)thiophen-2-yl]methylidene]-10-methoxy-2,2,4-trimethyl-1h-chromeno[3,4-f]quinolin-9-ol Chemical group C1=CSC(\C=C/2C3=C4C(C)=CC(C)(C)NC4=CC=C3C3=C(OC)C(O)=CC=C3O\2)=C1C(O)CCCC CMCZKWJUYJOKFX-IWIPYMOSSA-N 0.000 description 1
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 1
- 101710141544 Allatotropin-related peptide Proteins 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 240000007263 Pinus koraiensis Species 0.000 description 1
- 235000011615 Pinus koraiensis Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
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- 239000006185 dispersion Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000010931 ester hydrolysis Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002103 nanocoating Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
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- 238000005303 weighing Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides an adhesive for a lithium ion battery, which comprises a core, and a first coating layer and a second coating layer which are sequentially coated on the outer surface of the core, wherein the core is inorganic nano particles, the first coating layer comprises ethyl acrylate, polyvinyl alcohol, polyurethane and a first emulsifier, the second coating layer comprises a four-arm polyacrylic acid copolymer, modified carboxymethyl cellulose and a second emulsifier, and the mass ratio of the four-arm polyacrylic acid copolymer to the modified carboxymethyl cellulose is (1-3) to (5-8). According to the adhesive, the first coating layer and the second coating layer are sequentially coated with the inorganic nano particles, the core and the two coating layers are mutually matched, so that the requirement on the adhesive performance of a silicon anode can be met, the volume expansion of silicon can be obviously restrained, the silicon particles can keep relatively fixed positions, the elastic expansion of the silicon particles is realized, and the problem of rapid capacity attenuation of a lithium battery caused by the volume expansion of the silicon particles is effectively reduced.
Description
Technical Field
The invention relates to a binder for a lithium ion battery, in particular to a binder for a silicon negative electrode of a lithium ion battery and a preparation method thereof.
Background
Lithium ion batteries are widely applied to the fields of portable electronic equipment, electric automobiles and the like, and along with the continuous development of lithium ion battery technology, the weight reduction and miniaturization of electronic products are promoted. In the traditional lithium ion battery, graphite is generally selected as a negative electrode material, and the theoretical capacity of the graphite is low (372 mA h/g) and cannot meet the requirement of high energy density, so that the application of the graphite negative electrode in an electric automobile is also hindered. However, silicon (Si) can solve this problem as a negative electrode material instead of graphite, and is highly promising as a negative electrode material for next-generation lithium ion batteries because of its high theoretical capacity (4200 mA ·h/g).
However, the volume of the silicon particles expands (> 300%) during the cycling process, which results in structural pulverization of the electrode material and rapid decay of the capacity, thus limiting the practical application of the silicon-based anode in lithium batteries.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a binder for a lithium battery, which can effectively reduce the rapid capacity decay of the lithium battery caused by the volume expansion of silicon particles. Meanwhile, the invention also provides a preparation method of the binder and application of the binder in lithium batteries.
In order to achieve the above object, in one aspect, the present invention provides an adhesive for a lithium ion battery, the adhesive including a core, a first cladding layer and a second cladding layer sequentially coated on an outer surface of the core;
The first coating layer comprises ethyl acrylate, polyvinyl alcohol, polyurethane and a first emulsifier;
The second coating layer comprises a four-arm polyacrylic acid copolymer, modified carboxymethyl cellulose and a second emulsifier, and the mass ratio of the four-arm polyacrylic acid copolymer to the modified carboxymethyl cellulose is (1-3) (5-8).
The binder for the lithium ion battery comprises a core, and a first coating layer and a second coating layer which are sequentially coated on the outer surface of the core, wherein the core is made of inorganic nano particles, the first coating layer is made of ethyl acrylate, polyvinyl alcohol, polyurethane and a first emulsifier, and the second coating layer is made of a four-arm polyacrylic acid copolymer, modified carboxymethyl cellulose and a second emulsifier. In the adhesive, the core adopts inorganic nano particles to endow the adhesive core with certain rigidity, the first coating layer has proper elasticity through screening and blending of the raw materials, and the second coating layer selects the quadrifilar polyacrylic copolymer and the modified carboxymethyl cellulose with specific proportions, so that the adhesive performance requirement on the silicon negative electrode can be realized, and the volume expansion of silicon can be obviously restrained. The adhesive is designed through the overall structure of the core, the first coating layer and the second coating layer, the second coating layer has strong bonding effect on the silicon cathode, the core, the first coating layer and the second coating layer can effectively inhibit the volume expansion of silicon, and the fracture surface of the reconstruction material can be repaired after the volume expansion of silicon particles is mechanically damaged, so that the silicon particles are kept at a relatively fixed position, the elastic expansion of the silicon particles is realized, and the problem of the rapid capacity attenuation of the lithium battery caused by the volume expansion of the silicon particles is effectively reduced.
The four-arm polyacrylic acid copolymer is polyacrylic acid homopolymer (4A-PAA) with a four-arm molecular structure prepared by combining an ATRP polymerization technology with an ester hydrolysis method, and the synthetic method is shown in the specification LUO C, WU X F, ZHANG T, et al. A Four-Armed Polyacrylic Acid Homopolymer Binder with Enhanced Performance for SiOx/Graphite Anode[J]. Macromolecular Materials and Engineering, 2021, 306(1): 2000525.
Preferably, the modified carboxymethyl cellulose in the second coating layer is citric acid modified carboxymethyl cellulose. The citric acid modified carboxymethyl cellulose can be purchased in the market or self-made and the like. The preparation method of the citric acid modified carboxymethyl fiber comprises the following steps:
(1) Adding citric acid powder into a solvent, and stirring in a water bath to dissolve the citric acid powder to obtain a citric acid solution;
(2) Adding ultrapure water and carboxymethyl cellulose into a citric acid solution together, and stirring in a water bath for reaction to obtain the citric acid modified carboxymethyl cellulose.
Preferably, in the second coating layer, the sum of the mass percentages of the four-arm polyacrylic acid copolymer and the modified carboxymethyl cellulose is 50-80%. In the second coating layer, the sum of the mass percentages of the four-arm polyacrylic acid copolymer and the modified carboxymethyl cellulose is 50-80%, and if the sum of the mass percentages of the four-arm polyacrylic acid copolymer and the modified carboxymethyl cellulose is too small, the bonding performance of the silicon negative electrode is affected, and the inhibition effect on the volume expansion of the silicon negative electrode is obviously affected. If the content of the two is too high, the dispersion uniformity of the two in the second coating layer is affected, and the adhesive property and the suppression effect on the volume expansion of the silicon anode are also adversely affected. The sum of the mass percentages of the four-arm polyacrylic acid copolymer and the modified carboxymethyl cellulose can be, for example, 50%, 52%, 54%, 56%, 58%, 60%, 62%, 64%, 66%, 68%, 70%, 72%, 74%, 76%, 78%, 80% or any two point values. More preferably, in the second coating layer, the sum of the mass percentages of the four-arm polyacrylic acid copolymer and the modified carboxymethyl cellulose is 60-80%.
More preferably, the mass ratio of the four-arm polyacrylic acid copolymer to the modified carboxymethyl cellulose is 2 (5-8). The four-arm polyacrylic acid copolymer and the modified carboxymethyl cellulose have a combined assistance effect, and the four-arm polyacrylic acid copolymer has a multi-arm molecular structure, can reduce the molecular regularity and intramolecular hydrogen bond interaction of polyacrylic acid, and can enhance the toughness and the adhesive force of the adhesive. The modified carboxymethyl cellulose has a specific network structure, so that not only can the adhesive force of the adhesive be enhanced, but also the adhesive has a certain fixing effect on the silicon particles, and the relatively fixed position of the silicon particles is kept, thereby realizing the elastic expansion of the silicon particles. The inventor of the present application found in experiments that when the two are combined, the ratio of the two amounts has direct influence on the binding power of the binder and the effect of inhibiting the volume expansion of the silicon negative electrode, and if the ratio of the two amounts is too large or too small, the two amounts cannot have both the stronger binding power and the effect of inhibiting the volume expansion of the silicon negative electrode, and when the two amounts are in a proper ratio range, the high binding power and the effect of inhibiting the volume expansion of the silicon particles can be realized.
Preferably, the inorganic nano particles are at least one of sodium tripolyphosphate powder, silicon dioxide nano particles and titanium dioxide nano particles, and the particle size of the sodium tripolyphosphate powder is 1-1000 nm. More preferably, the particle size of the sodium tripolyphosphate powder is 100-600 nm.
Preferably, the first emulsifier and the second emulsifier are each independently selected from at least one of octyl phenol polyoxyethylene ether, polyoxyethylene-8-octyl phenyl ether and oleic acid polyoxyethylene ether. More preferably, the first emulsifier and the second emulsifier are mixtures of octyl phenol polyoxyethylene ether and oleic acid polyoxyethylene ether, and the mass ratio of the first emulsifier to the second emulsifier is preferably but not limited to (1-4): 1.
Preferably, the sum of the mass percentages of the ethyl acrylate, the polyvinyl alcohol and the polyurethane in the first coating layer is 65-85%. The total content of ethyl acrylate, polyvinyl alcohol and polyurethane in the first coating layer is too low, and the performances such as elasticity and the like of the first coating layer are influenced, so that the inhibition effect on the volume expansion of the silicon anode is directly influenced. More preferably, the sum of the mass percentages of the ethyl acrylate, the polyvinyl alcohol and the polyurethane in the first coating layer is 70-80%.
Preferably, the mass ratio of the ethyl acrylate to the polyvinyl alcohol to the polyurethane in the first coating layer is 5 (2-3): 1. The inventor discovers that the ethyl acrylate, the polyvinyl alcohol and the polyurethane in the first coating layer need to be in a proper amount ratio to enable the first coating layer to be tightly attached to the core and the second coating layer, and the first coating layer has proper elasticity and other properties, so that a synergistic inhibition effect on the volume expansion of the silicon negative electrode is realized.
Preferably, the mass ratio of the core to the first coating layer to the second coating layer is (1-3) to (2-5) of (first coating layer+second coating layer) = (first coating layer+second coating layer).
Preferably, the mass ratio of the first coating layer to the second coating layer is (1-2): 1.
The core, the first coating layer and the second coating layer have direct influence on the bonding performance of the adhesive and the inhibition and restoration effect on the volume expansion of the silicon negative electrode, and after screening and determining the raw materials of the first coating layer and the second coating layer, the inventor discovers that the core and the two coating layers meet the requirement that the core is formed by the mass sum of the two coating layers is (1-3): 2-5, more preferably (3-5), and the core and the two coating layers are matched with each other when the mass sum of the two coating layers is (1-3): 2-5, so that the inhibition effect on the volume expansion of the silicon negative electrode material is more remarkable. The mass ratio of the first coating layer to the second coating layer also has direct influence on the cohesive force of the adhesive and the inhibition effect of the volume expansion of the silicon negative electrode, and preferably, the mass ratio of the first coating layer to the second coating layer is (1-2): 1, and the adhesive has excellent comprehensive performance by matching the two materials.
In order to achieve the purpose, the invention adopts the technical scheme that the preparation method of the adhesive for the lithium ion battery comprises the following steps:
(1) Mixing all substances contained in the first coating layer to obtain a first coating layer emulsion;
(2) Mixing the first coating emulsion with inorganic nano particles and coating to obtain a binder precursor;
(3) And mixing all substances contained in the second coating layer to obtain second coating layer emulsion, and then mixing the second coating layer emulsion with a binder precursor for coating to obtain the binder.
Finally, the invention also provides application of the binder in a lithium ion battery. The binder provided by the invention can effectively reduce the problem of rapid capacity decay of the lithium battery caused by volume expansion of silicon particles, and is particularly suitable for being used as a binder for a silicon negative electrode.
According to the adhesive, the first coating layer and the second coating layer which are made of specific components are sequentially coated with the inorganic nano particles, and the core and the two coating layers are mutually matched, so that the adhesive can not only meet the requirement on the adhesive performance of a silicon negative electrode, but also obviously inhibit the volume expansion of silicon, so that the silicon particles keep relatively fixed positions, the elastic expansion of the silicon particles is realized, and the problem of rapid capacity attenuation of a lithium battery caused by the volume expansion of the silicon particles is effectively reduced.
Drawings
FIG. 1 is a graph of average peel strength versus comparative adhesive for examples of the present invention;
FIG. 2 is a graph showing a comparison of first coulombic efficiencies of cells prepared with the binders of examples and comparative examples of the present invention;
Fig. 3 is a graph showing the specific discharge capacity of 200 cycles of battery cycles prepared from the binders according to the examples and comparative examples of the present invention.
Detailed Description
Unless otherwise specified, the raw materials used in the examples of the present invention are commercially available conventional raw materials, the equipment used is conventional equipment in the art, and the methods used are conventional methods in the art. For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples, but should not be construed as limiting the invention in any way.
The sources of the raw materials used in the following examples are as follows:
Sodium tripolyphosphate powder with particle size of 100-200nm purchased from Liangde nanometer powder Innovative technology (Anhui) Co., ltd;
Ethyl acrylate, purchased from Shandong Chuang chemical Co., ltd;
polyvinyl alcohol from Pinus koraiensis chemical Co., ltd;
polyurethane is purchased from the scientific and technological company of Chengcheng new materials in Dongguan;
Octyl phenol polyoxyethylene ether (OP-10) available from the sea Ann petrochemical plant of Jiangsu province;
oleic acid polyoxyethylene ether is purchased from Jiangsu province sea-An petrochemical plant;
the synthesis of the four-arm polyacrylic acid copolymer used in the examples below is described in LUO C, WU X F, ZHANG T, et al. A Four-Armed Polyacrylic Acid Homopolymer Binder with Enhanced Performance for SiOx/Graphite Anode[J]. Macromolecular Materials and Engineering, 2021, 306(1): 2000525.
The citric acid modified carboxymethyl cellulose used in the examples below may be purchased commercially or homemade using existing conventional methods, including, for example, but not limited to:
(1) Weighing 0.05g of citric acid powder, adding into 2ml of ethanol, stirring in a 50 ℃ water bath for 30min to fully dissolve the citric acid powder, and obtaining a citric acid alcohol solution;
(2) 2ml of ultrapure water is weighed, 0.05g of carboxymethyl cellulose is weighed and added into the citric acid alcohol solution in the step (1) together, and the mixture is stirred in a water bath at 50 ℃ for 1 day, so that the citric acid modified carboxymethyl cellulose is finally obtained.
Embodiment 1 of the binder for a lithium ion battery, which is an embodiment of the binder for a lithium ion battery, comprises a core, a first coating layer and a second coating layer which are sequentially coated on the outer surface of the core, wherein the core, the first coating layer and the second coating layer comprise the following components in parts by weight:
Core, 100 parts of sodium tripolyphosphate powder;
the first coating layer comprises 50 parts of ethyl acrylate, 20 parts of polyvinyl alcohol, 10 parts of polyurethane, 10 parts of octyl phenol polyoxyethylene ether (OP-10) and 10 parts of oleic acid polyoxyethylene ether;
the second coating layer comprises 10 parts of quadrifilar polyacrylic acid copolymer, 40 parts of citric acid modified carboxymethyl cellulose, 25 parts of octyl phenol polyoxyethylene ether (OP-10) and 25 parts of oleic acid polyoxyethylene ether.
The adhesive in this example was prepared by the following method:
(1) Mixing all substances contained in the first coating layer to obtain a first coating layer emulsion;
(2) Mixing and coating the first coating emulsion with sodium tripolyphosphate powder to obtain a binder precursor;
(3) And mixing all substances contained in the second coating layer to obtain second coating layer emulsion, and then mixing the second coating layer emulsion with the binder precursor for coating to obtain the binder of the embodiment.
Embodiment 2 of the binder for a lithium ion battery according to the present invention, the binder includes a core, and a first coating layer and a second coating layer sequentially coated on an outer surface of the core, where the core, the first coating layer and the second coating layer include the following components in parts by weight:
Core, 100 parts of sodium tripolyphosphate powder;
the first coating layer comprises 80 parts of ethyl acrylate, 48 parts of polyvinyl alcohol, 16 parts of polyurethane, 28 parts of octyl phenol polyoxyethylene ether (OP-10) and 28 parts of oleic acid polyoxyethylene ether;
The second coating layer comprises 18 parts of a quadrifilar polyacrylic acid copolymer, 42 parts of citric acid modified carboxymethyl cellulose, 20 parts of octyl phenol polyoxyethylene ether (OP-10) and 20 parts of oleic acid polyoxyethylene ether.
The binder of this example was prepared in the same manner as in example 1.
Embodiment 3 of the binder for a lithium ion battery according to the present invention, the binder includes a core, and a first coating layer and a second coating layer sequentially coated on an outer surface of the core, where the core, the first coating layer and the second coating layer include the following components in parts by weight:
Core, 100 parts of sodium tripolyphosphate powder;
the first coating layer comprises 120 parts of ethyl acrylate, 48 parts of polyvinyl alcohol, 24 parts of polyurethane, 29 parts of octyl phenol polyoxyethylene ether (OP-10) and 29 parts of oleic acid polyoxyethylene ether;
The second coating layer comprises 20 parts of quadrifilar polyacrylic acid copolymer, 120 parts of citric acid modified carboxymethyl cellulose, 55 parts of octyl phenol polyoxyethylene ether (OP-10) and 55 parts of oleic acid polyoxyethylene ether.
The binder of this example was prepared in the same manner as in example 1.
Embodiment 4 of the binder for a lithium ion battery, which is an embodiment of the binder for a lithium ion battery, comprises a core, a first coating layer and a second coating layer which are sequentially coated on the outer surface of the core, wherein the core, the first coating layer and the second coating layer comprise the following components in parts by weight:
Core, 100 parts of sodium tripolyphosphate powder;
The first coating layer comprises 22.5 parts of ethyl acrylate, 13.5 parts of polyvinyl alcohol, 4.5 parts of polyurethane, 5 parts of octyl phenol polyoxyethylene ether (OP-10) and 4.5 parts of oleic acid polyoxyethylene ether;
the second coating layer comprises 15 parts of a quadrifilar polyacrylic acid copolymer, 25 parts of citric acid modified carboxymethyl cellulose, 5 parts of octyl phenol polyoxyethylene ether (OP-10) and 5 parts of oleic acid polyoxyethylene ether.
The binder of this example was prepared in the same manner as in example 1.
Embodiment 5. The binder for a lithium ion battery according to the present invention comprises a core, and a first coating layer and a second coating layer sequentially coated on the outer surface of the core, wherein the core, the first coating layer and the second coating layer comprise the following components in parts by weight:
200 parts of core, namely sodium tripolyphosphate powder;
the first coating layer comprises 105 parts of ethyl acrylate, 42 parts of polyvinyl alcohol, 21 parts of polyurethane, 41 parts of octyl phenol polyoxyethylene ether (OP-10) and 41 parts of oleic acid polyoxyethylene ether;
The second coating layer comprises 50 parts of quadrifilar polyacrylic acid copolymer, 125 parts of citric acid modified carboxymethyl cellulose, 50 parts of octyl phenol polyoxyethylene ether (OP-10) and 25 parts of oleic acid polyoxyethylene ether.
The binder of this example was prepared in the same manner as in example 1.
Embodiment 6 of the binder for a lithium ion battery, which is an embodiment of the binder for a lithium ion battery, comprises a core, a first coating layer and a second coating layer which are sequentially coated on the outer surface of the core, wherein the core, the first coating layer and the second coating layer comprise the following components in parts by weight:
core, 300 parts of sodium tripolyphosphate powder;
The first coating layer comprises 47 parts of ethyl acrylate, 28 parts of polyvinyl alcohol, 10 parts of polyurethane, 10 parts of octyl phenol polyoxyethylene ether (OP-10) and 5 parts of oleic acid polyoxyethylene ether;
The second coating layer comprises 7 parts of quadrifilar polyacrylic acid copolymer, 56 parts of citric acid modified carboxymethyl cellulose, 30 parts of octyl phenol polyoxyethylene ether (OP-10) and 7 parts of oleic acid polyoxyethylene ether.
The binder of this example was prepared in the same manner as in example 1.
Embodiment 7 of the binder for a lithium ion battery, which is an embodiment of the binder for a lithium ion battery, comprises a core, a first coating layer and a second coating layer which are sequentially coated on the outer surface of the core, wherein the core, the first coating layer and the second coating layer comprise the following components in parts by weight:
core, 300 parts of sodium tripolyphosphate powder;
The first coating layer comprises 125 parts of ethyl acrylate, 50 parts of polyvinyl alcohol, 25 parts of polyurethane, 50 parts of octyl phenol polyoxyethylene ether (OP-10) and 50 parts of oleic acid polyoxyethylene ether;
The second coating layer comprises 30 parts of a quadrifilar polyacrylic acid copolymer, 80 parts of citric acid modified carboxymethyl cellulose, 45 parts of octyl phenol polyoxyethylene ether (OP-10) and 45 parts of oleic acid polyoxyethylene ether.
The binder of this example was prepared in the same manner as in example 1.
Embodiment 8 of the binder for a lithium ion battery according to the present invention, the binder includes a core, a first coating layer and a second coating layer sequentially coated on an outer surface of the core, wherein the core, the first coating layer and the second coating layer comprise the following components in parts by weight:
83 parts of sodium tripolyphosphate powder;
the first coating layer comprises 120 parts of ethyl acrylate, 48 parts of polyvinyl alcohol, 24 parts of polyurethane, 29 parts of octyl phenol polyoxyethylene ether (OP-10) and 29 parts of oleic acid polyoxyethylene ether;
The second coating layer comprises 20 parts of quadrifilar polyacrylic acid copolymer, 120 parts of citric acid modified carboxymethyl cellulose, 55 parts of octyl phenol polyoxyethylene ether (OP-10) and 55 parts of oleic acid polyoxyethylene ether.
The binder of this example was prepared in the same manner as in example 1.
Embodiment 9 of the binder for a lithium ion battery, which is an embodiment of the binder for a lithium ion battery, comprises a core, a first coating layer and a second coating layer which are sequentially coated on the outer surface of the core, wherein the core, the first coating layer and the second coating layer comprise the following components in parts by weight:
Core, 1000 parts of sodium tripolyphosphate powder;
the first coating layer comprises 120 parts of ethyl acrylate, 48 parts of polyvinyl alcohol, 24 parts of polyurethane, 29 parts of octyl phenol polyoxyethylene ether (OP-10) and 29 parts of oleic acid polyoxyethylene ether;
The second coating layer comprises 20 parts of quadrifilar polyacrylic acid copolymer, 120 parts of citric acid modified carboxymethyl cellulose, 55 parts of octyl phenol polyoxyethylene ether (OP-10) and 55 parts of oleic acid polyoxyethylene ether.
The binder of this example was prepared in the same manner as in example 1.
Comparative example 1. A comparative example of an adhesive for a lithium ion battery according to the present invention comprises a core and a first coating layer coated on the outer surface of the core, wherein the core and the first coating layer comprise the following components in parts by weight:
Core, 100 parts of sodium tripolyphosphate powder;
the first coating layer comprises 50 parts of ethyl acrylate, 20 parts of polyvinyl alcohol, 10 parts of polyurethane, 10 parts of octyl phenol polyoxyethylene ether (OP-10) and 10 parts of oleic acid polyoxyethylene ether.
The adhesive in this example was prepared by the following method:
(1) Mixing all substances contained in the first coating layer to obtain a first coating layer emulsion;
(2) And mixing the first coating emulsion with sodium tripolyphosphate powder and coating to obtain the adhesive of the comparative example.
Comparative example 2A comparative example of an adhesive for a lithium ion battery according to the present invention, the adhesive comprises a core and a first coating layer coated on the outer surface of the core, wherein the core and the first coating layer comprise the following components in parts by weight:
Core, 100 parts of sodium tripolyphosphate powder;
the first coating layer comprises 10 parts of a four-arm polyacrylic acid copolymer, 40 parts of citric acid modified carboxymethyl cellulose, 25 parts of octyl phenol polyoxyethylene ether (OP-10) and 25 parts of oleic acid polyoxyethylene ether.
The adhesive in this example was prepared by the following method:
(1) Mixing all substances contained in the first coating layer to obtain a first coating layer emulsion;
(2) And mixing the first coating emulsion with sodium tripolyphosphate powder and coating to obtain the adhesive of the comparative example.
Comparative example 3A comparative example of an adhesive for a lithium ion battery according to the present invention, the adhesive comprises a core, a first coating layer and a second coating layer sequentially coated on the outer surface of the core, wherein the core, the first coating layer and the second coating layer comprise the following components in parts by weight:
Core, 100 parts of sodium tripolyphosphate powder;
the first coating layer comprises 10 parts of a quadrifilar polyacrylic acid copolymer, 40 parts of citric acid modified carboxymethyl cellulose, 25 parts of octyl phenol polyoxyethylene ether (OP-10) and 25 parts of oleic acid polyoxyethylene ether;
The second coating layer comprises 50 parts of ethyl acrylate, 20 parts of polyvinyl alcohol, 10 parts of polyurethane, 10 parts of octyl phenol polyoxyethylene ether (OP-10) and 10 parts of oleic acid polyoxyethylene ether.
The preparation method of this comparative example is the same as in example 1.
Comparative example 4A comparative example of an adhesive for a lithium ion battery according to the present invention, the adhesive comprises a core, a first coating layer and a second coating layer sequentially coated on the outer surface of the core, wherein the core, the first coating layer and the second coating layer comprise the following components in parts by weight:
Core, 100 parts of sodium tripolyphosphate powder;
the first coating layer comprises 50 parts of ethyl acrylate, 20 parts of polyvinyl alcohol, 10 parts of polyurethane, 10 parts of octyl phenol polyoxyethylene ether (OP-10) and 10 parts of oleic acid polyoxyethylene ether;
And the second coating layer comprises 50 parts of citric acid modified carboxymethyl cellulose, 25 parts of octyl phenol polyoxyethylene ether (OP-10) and 25 parts of oleic acid polyoxyethylene ether.
The preparation method of this comparative example is the same as in example 1.
Comparative example 5A comparative example of an adhesive for a lithium ion battery according to the present invention, the adhesive comprises a core, a first coating layer and a second coating layer sequentially coated on the outer surface of the core, wherein the core, the first coating layer and the second coating layer comprise the following components in parts by weight:
Core, 100 parts of sodium tripolyphosphate powder;
the first coating layer comprises 50 parts of ethyl acrylate, 20 parts of polyvinyl alcohol, 10 parts of polyurethane, 10 parts of octyl phenol polyoxyethylene ether (OP-10) and 10 parts of oleic acid polyoxyethylene ether;
The second coating layer comprises 50 parts of quadrifilar polyacrylic acid copolymer, 25 parts of octyl phenol polyoxyethylene ether (OP-10) and 25 parts of oleic acid polyoxyethylene ether.
Effect example 1 adhesive property test of adhesive for lithium Battery according to the present invention
The binders prepared in examples 1 to 9 and comparative examples 1 to 5 were used to prepare silicon negative electrode sheets, and the preparation method of each group of silicon negative electrode sheets was as follows:
And fully mixing the silicon nano particles, the binder and the conductive carbon black in a high-speed oscillating ball mill according to a mass ratio of 7:2:1, uniformly coating the mixture on a copper foil, and then drying the mixture at 60 ℃ for 6 hours and then drying the mixture at 120 ℃ for 12 hours in a vacuum environment to obtain the silicon negative electrode sheet.
And (3M adhesive tapes of 24mm are stuck on the surfaces of the prepared silicon negative plates (5 are taken from each group), and weights of 200g are used for uniformly pushing the adhesive tapes, so that the adhesive tapes are ensured to be uniformly stressed. One end of the adhesive tape and the silicon negative electrode plate were fixed by a clamp of a universal tensile machine, the adhesive tape was pulled at a speed of 10mm/min, the peeling condition of the silicon negative electrode plate was observed, the peeling strength of each group of silicon negative electrode plates was recorded, and the average value of each group was taken, and the results are shown in table 1 and fig. 1.
As can be seen from the results in Table 1, examples 1 to 9 all have a strong peel strength, and the adhesives of examples 1 to 9 in the specification have good adhesive properties. Comparative example 1 differs from example 1 only in that the first coating layer in example 1 is not contained, and comparative example 1 also has a higher peel strength, indicating that the adhesive properties of the adhesive according to the present invention are mainly brought about by the second coating layer. Comparative examples 2 and 3 are different from example 1 mainly in that the outermost layer of the adhesive is a first coating layer instead of a second coating layer, and as is evident from the significant decrease in peel strength of comparative examples 2 and 3 compared to example 1, the adhesive properties of the first coating layer in the adhesive of the present invention are much lower than those of the second coating layer. The main difference between comparative examples 4 and 5 and example 1 is that the second coating layer contains only one of the four-arm polyacrylic acid copolymer and the citric acid-modified carboxymethyl cellulose, and it is clear from comparison of the peel strengths of comparative examples 4 and 5 with example 1 that the combination of the four-arm polyacrylic acid copolymer and the citric acid-modified carboxymethyl cellulose has a synergistic effect on the adhesive property of the adhesive.
Effect example 2 electrochemical properties of lithium batteries prepared using the binders of the present invention
The performance of the battery was checked by assembling the button half cell CR 2032. The silicon negative electrode sheets prepared in examples 1 to 9 and comparative examples 1 to 5 of effect example 1 were used as working electrodes, and lithium metal sheets (15 mm. Times.0.6 mm) were used as counter electrodes, respectively, and a battery case group (CR 2032), a stainless steel gasket (thickness 1 mm), and a spring sheet (thickness 1 mm).
The CR2032 battery is assembled by cutting electrode plate after vacuum drying at 120deg.C into round electrode plate with diameter of 1.54 cm 2. And the button battery is assembled in a glove box filled with argon, the environment of the glove box is strictly controlled under the conditions of water pressure and oxygen pressure lower than 1ppm, and lithium metal oxidation is prevented. The method comprises the steps of assembling a positive electrode shell, a silicon negative electrode, a diaphragm, a metal lithium sheet, a stainless steel gasket, a spring sheet and a negative electrode shell in sequence, adding 0.1mL of electrolyte, dissolving 1mol/L of lithium hexafluorophosphate (LiPF 6 ) in a 1:1 volume ratio of Ethylene Carbonate (EC) and diethyl carbonate (DEC) solvent, adding 10% by mass of fluoroethylene carbonate (FEC), and performing pressure sealing on a CR2032 battery by using a button cell sealing machine, wherein the sealing pressure is 1000 psi, so as to obtain a CR2032 half battery, and standing for 12h for electrochemical performance testing.
The blue electric battery detection system is used for testing the electrochemical performance of the button half battery, the temperature is 25 ℃, the voltage range is 0.01-1.2V, the test method is that 3 circles are activated under the current density of 0.1C, 200 circles are circulated under the current density of 0.2C, the scanning rate of the cyclic voltammetry (Cyclic Voltammetry, CV) test is 0.2 mV/s, and the potential interval is 0.01-3.0V.
The results of the initial coulombic efficiency and specific discharge capacity for 200 cycles at a current density of 0.2C for each set of cells are shown in table 2 and figures 2 and 3.
As can be seen from the results of table 2, the battery assembled from the silicon negative electrode sheet prepared by the binder of the present invention has more excellent electrochemical properties.
As can be seen from comparison of comparative examples 1 to 3 with example 1, the adhesive of the present invention comprises a core, a first coating layer and a second coating layer in a certain order, and the three layers together achieve the effect of improving the electrochemical performance of the silicon negative electrode sheet.
As can be seen from comparison of comparative examples 4 and 5 with example 1, in the adhesive according to the present invention, the combination of the four-arm polyacrylic acid copolymer and the citric acid modified carboxymethyl cellulose in the second coating layer can further maintain the silicon particles at a relatively fixed position, thereby effectively solving the problem of rapid capacity decay of the lithium battery caused by volume expansion of the silicon particles.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
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