CN103337656B - A kind of modified biomass Li-like ions battery adhesive - Google Patents
A kind of modified biomass Li-like ions battery adhesive Download PDFInfo
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- CN103337656B CN103337656B CN201310279932.XA CN201310279932A CN103337656B CN 103337656 B CN103337656 B CN 103337656B CN 201310279932 A CN201310279932 A CN 201310279932A CN 103337656 B CN103337656 B CN 103337656B
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 27
- 239000000853 adhesive Substances 0.000 title claims abstract description 26
- 239000002028 Biomass Substances 0.000 title claims abstract description 16
- 150000002500 ions Chemical class 0.000 title claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 10
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 8
- 229920001661 Chitosan Polymers 0.000 claims abstract description 7
- 229920005615 natural polymer Polymers 0.000 claims abstract description 6
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 5
- 239000000661 sodium alginate Substances 0.000 claims abstract description 5
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 5
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims abstract description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims abstract description 5
- 229920002101 Chitin Polymers 0.000 claims abstract description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052710 silicon Inorganic materials 0.000 claims abstract 2
- 239000010703 silicon Substances 0.000 claims abstract 2
- 239000000758 substrate Substances 0.000 claims abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910021385 hard carbon Inorganic materials 0.000 claims description 3
- 229910021382 natural graphite Inorganic materials 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 2
- 239000002931 mesocarbon microbead Substances 0.000 claims description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims 4
- 239000003575 carbonaceous material Substances 0.000 claims 1
- 238000001704 evaporation Methods 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 17
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 17
- 229920000856 Amylose Polymers 0.000 abstract description 3
- 235000010489 acacia gum Nutrition 0.000 abstract description 3
- 239000001785 acacia senegal l. willd gum Substances 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 2
- 230000032050 esterification Effects 0.000 abstract description 2
- 238000005886 esterification reaction Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 230000004888 barrier function Effects 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 9
- -1 lithium hexafluoro phosphates Chemical class 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 6
- 229920002521 macromolecule Polymers 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000000025 haemostatic effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- LKAPTZKZHMOIRE-KVTDHHQDSA-N (2s,3s,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)oxolane-2-carbaldehyde Chemical compound OC[C@H]1O[C@H](C=O)[C@@H](O)[C@@H]1O LKAPTZKZHMOIRE-KVTDHHQDSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229940030225 antihemorrhagics Drugs 0.000 description 2
- LKAPTZKZHMOIRE-UHFFFAOYSA-N chitose Natural products OCC1OC(C=O)C(O)C1O LKAPTZKZHMOIRE-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000007058 Halophila ovalis Species 0.000 description 1
- 208000032843 Hemorrhage Diseases 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 150000007516 brønsted-lowry acids Chemical class 0.000 description 1
- 150000007528 brønsted-lowry bases Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012611 container material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000023597 hemostasis Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000018729 macromolecule modification Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical class O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a kind of preparation method of modified biomass Li-like ions battery adhesive, by to multiple natural polymers such as sodium carboxymethylcellulose, sodium alginate, amylose, Arabic gum, carboxymethyl chitin, carboxymethyl chitosan etc. under elevated temperature in vacuo carry out esterification and crosslinking with polyacrylic acid or polymethylacrylic acid and a series of adhesive for lithium ion battery have been obtained.When adhesive prepared by the present invention is applied to the lithium ion battery negative material of carbon-based and silicon substrate, consumption seldom can just reach good bonding effect, the film forming of material can be significantly improved, and have raw material cheap and easy to get, preparation method is simple, the advantages of environmentally friendly pollution-free.
Description
Technical field
The invention belongs to adhesive for lithium ion battery field, is related to class environment-friendly biomass Li-like ions battery bonding
The preparation and application of agent.
Background technology
Biomass refer to the general name of all biologic artifacts produced by photosynthesis, give up including plant, crops, forest products
Gurry, marine products（Various sea grass）With urban waste etc., wherein sodium carboxymethylcellulose, sodium alginate, amylose, I
Primary glue, carboxymethyl chitin, carboxymethyl chitosan etc. belong to Biodegradable material of the natural materials using type, and these belong to
Renewable resource, few to resource and energy resource consumption, environmentally friendly and cheap, and health is not affected.
Improve biological material machinability such as film forming or to its modification application in industrial production to environment and
Economy is all significant, and particularly biomass macromolecular material is all obtained in a lot of fields such as medical science, chemistry, biology in the last few years
To being widely applied, such as patent CN1935884 has been obtained a kind of starch-modified plasticizing adjuvant, for manufacturing " starch base heat
Plasticity biodegradation material " (sheet material or pellet), obtained material may replace partly plastic, be widely used in disposable meal
Tool, toy for children, without anti-cloth, personal hygiene article, all kinds of industrial or agricultural films, footwear packaging and non-returnable container material etc. lead
Domain, is the preferable substitute of Phthalates.Patent CN101081308 discloses a kind of chitose haemostatic, is by can
Be dissolve or swell in solid chitosan and the solid composite made of solid acid of acid, with hemostasis quick, closed group can be bonded
Knit wound, especially good to the haemostatic effect compared with massive haemorrhage chitose haemostatic.
There is certain viscosity as natural polymerses are dissolved in after water, therefore biomass natural polymer is changed
Property is applied to binding agent, and not only economical but also environmental protection, such as CN200610019568.3 disclose one kind with natural or modified beans
Albumen is obtained resistance to water with the blending of aqueous reinforced resin by method of the starch for adhesive chief component, US0089418AL
Preferable adhesive, CN102898987A have been obtained a kind of esterification starch modified urea-formaldehyde gluing agent, adhesion strength 3.0～
5.0MPa between.
In lithium ion battery, although the consumption of adhesive is less, but normal life of its adhesive property to lithium ion battery
Produce and final performance all has a significant impact, be a kind of important auxiliary material of battery industry, generally its consumption accounts for positive and negative electrode work
The 5%-8% of property material.The adhesive for lithium ion battery that commonly uses in lithium ion battery industrial production at present is Kynoar
（PVDF）Homopolymers and copolymer, as PVDF needs to use 1-METHYLPYRROLIDONE, N, N- dimethylformamide, dimethyl are sub-
Sulfone etc. makees solvent, not only pollutes environment, and harm staff is healthy and makes battery cost up with organic solvent.To biomass
Class natural macromolecule modification and to obtain a kind of aqueous lithium ion battery binding agent all significant to environment and economy, for example
With acrylic acid or acrylate after in patent CN102876266A be modified starch under the alternating action of binary bronsted lowry acids and bases bronsted lowry
Emulsion carries out enhancing and obtains a kind of environment-friendlyadhesive adhesive for lithium ion battery, and polyacrylic acid or polymethylacrylic acid are a lot of bondings
The important component part of agent, makes it have stronger caking property due to forming hydrogen bond between carboxyl.Due to sodium alginate, directly
The biomass macromolecule such as chain starch, Arabic gum, carboxymethyl chitin, carboxymethyl chitosan is that straight chain molecule caking property is limited,
And as between molecule, between hydroxyl, hydrogen bond action is by force after electrode material mixing that film forming is poor very much, therefore we are by poly- third
Olefin(e) acid and polymethylacrylic acid are connected on these macromolecules and on the one hand make it have certain degree of cross linking negative material is twined
Strengthen around property, on the other hand introduce some carboxylic groups weak with some hydrogen bonds etc. being formed between carboxyl and negative material molecule excessively
Intermolecular force increases so as to caking ability, while coating after the hydrogen bond destroyed between hydroxyl makes which mix with electrode material
Can improve.
Content of the invention
Problem solved by the invention is to provide a kind of environment-friendly biomass Li-like ions battery adhesive of low cost, this
Kind of adhesive for lithium ion battery has good water solubility in bonded-electrode material, low consumption, the advantages of viscosity is high.
In order to solve the above problems, the present invention is achieved by the following technical solutions, the preparation of adhesive：By biomass
Macromolecule and polyacrylic acid or polymethylacrylic acid are dissolved in a small amount of water, after the gel that stirs are dried moisture, with 150
Degree Celsius vacuum condition dissolves 1-5 hours makes the hydroxyl on biomass macromolecule mutually hand over polyacrylic acid or polymethylacrylic acid
Ester bond is unified into, wherein biomass macromolecule includes sodium carboxymethylcellulose, amylose, sodium alginate, Arabic gum, biomass
Macromolecule is 1 with the weight ratio of polyacrylic acid or polymethylacrylic acid:0.1-1:1.
Adhesive prepared by the present invention can apply to include native graphite, modified natural graphite, Delanium, centre
The negative materials such as phase carbon microspheres, CNT, graphitized carbon fibre, hard carbon, soft charcoal, Graphene, silica-base material, and be not limited to
Negative material is stated, and the optimum weight ratio that electrode material is accounted for during use is 2%-10%.
Binding agent filming performance prepared by the present invention is good, can improve the coating of negative material with electrode material after mixing
Energy.
The electrode material adhesive of the present invention, its battery performance and application, in the conventional method in this area, that is, are assembled into button
Formula half-cell and full battery carry out charge-discharge test investigation.Prepare and test process is as follows：
First by 6 grams of negative materials such as native graphite, modified natural graphite, Delanium, MCMB, carbon nanometer
The negative materials such as pipe, graphitized carbon fibre, hard carbon, soft charcoal, Graphene, silica-base material, are added followed by 6.30 gram mass fractions
For 5% binder solution, stir and form uniform negative pole slip.The slip is uniformly coated on Copper Foil, then 120 DEG C
Lower drying, roll-in, it is 12 millimeters that punching is obtained radius, and thickness is 80 microns of circular negative plate.At a temperature of 120-150 degree
After vacuum drying, being placed in the glove box of dry argon gas atmosphere, button half-cell being assembled into metal lithium electrode pairing, electrolyte is used
1M lithium hexafluoro phosphates（EC/DMC/EMC=1:1：1(v)）, barrier film is polypropylene.
Specific embodiment
With reference to specific embodiment, the present invention will be further described, but the present invention is not limited to following examples.
Embodiment 1：
1g sodium carboxymethylcelluloses and 0.5g polyacrylic acid are dissolved in 20mL water and are stirred 1 hour, after gel is uniform
Moisture is dried, is kept for two hours under molten state in 150 degrees Celsius of vacuum drying ovens, needed for obtaining after Temperature fall to room temperature
Lithium ion battery binding agent.
Embodiment 2：
Take after 0.5g is dissolved in 10mL water, plus 10g modified natural graphites by adhesive prepared by embodiment 1 and stir to be formed
After cathode size, with the slip is uniformly coated on Copper Foil, then dry at 120 DEG C, roll-in, it is 12 that punching is obtained radius
Millimeter, thickness is 80 microns of circular negative plate, after being vacuum dried, is placed in the gloves of dry argon gas atmosphere at a temperature of 120 degree
In case, half-cell, electrolyte 1M lithium hexafluoro phosphates is assembled into metal lithium electrode pairing（EC/DMC=1:1(v)）, barrier film use
Polypropylene barrier film, this adhesive prepare the discharge and recharge under 0.2C electric currents of lithium ion half-cell, first reversible capacity reach 355mAh/
More than g, and electrode is without dropping off phenomenon.
With cobalt acid lithium as positive pole, electrolyte 1M lithium hexafluoro phosphates（EC/DMC/EMC=1:1：1(v)）, barrier film polypropylene
Battery helped by barrier film, assembling, and with 10C discharge capacities as the 95% of 1C discharge capacities and electric 300 times with 1C current charge-discharges, capacity is protected
Holdup >=93%, after battery is disassembled, nothing drops off phenomenon.Under the conditions of same test compared with common PVDF, circulation is significantly improved
Performance, and nothing drops off phenomenon after battery is disassembled.
Embodiment 3：
Take after 0.6g is dissolved in 10mL water, plus 10g Si-C composite materials by adhesive prepared by embodiment 1 and stir to be formed
After cathode size, with the slip is uniformly coated on Copper Foil, then dry at 120 DEG C, roll-in, it is 12 that punching is obtained radius
Millimeter, thickness is 80 microns of circular negative plate, after being vacuum dried, is placed in the gloves of dry argon gas atmosphere at a temperature of 120 degree
In case, half-cell, electrolyte 1M lithium hexafluoro phosphates is assembled into metal lithium electrode pairing（EC/DMC/EMC=1:1：1(v)）,
Barrier film polypropylene barrier film, this adhesive prepare the discharge and recharge under 0.2C electric currents of lithium ion half-cell, first reversible capacity reach
950mAh/g, and electrode is without dropping off phenomenon.
With ternary material as positive pole, electrolyte 1M lithium hexafluoro phosphates（EC/DMC/EMC=1:1：1(v)）, barrier film is with poly- third
Battery helped by dilute barrier film, assembling, with 10C discharge capacities as the 95.5% of 1C discharge capacities and electric 300 times with 1C current charge-discharges, holds
Amount conservation rate >=94%, after battery is disassembled, nothing drops off phenomenon.Under the conditions of same test compared with common PVDF, significantly improve
Cycle performance, and nothing drops off phenomenon after battery is disassembled.
Embodiment 4：
1g carboxymethyl chitosans and 0.5g polyacrylic acid are dissolved in 20mL water and are stirred 1 hour, will after gel is uniform
Moisture is dried, and is kept for two hours under molten state in 120 degrees Celsius of vacuum drying ovens, needed for obtaining after Temperature fall to room temperature
Lithium ion battery binding agent.
Embodiment 5：
Take 0.5g and 10mL water is dissolved in by adhesive prepared by embodiment 4, the negative material in embodiment 2 is changed to mesophase
Carbon microspheres, positive electrode are changed to LiFePO4, and remaining is with embodiment with the lithium ion battery prepared with this adhesive is filled in 0.2C
Under discharging condition, the reversible capacity first of half-cell reaches 330mAh/g, and full battery 10C discharge capacities are the 96% of 1C discharge capacities,
And, capability retention >=95% electric 300 times with 1C current charge-discharges, after battery is disassembled, nothing drops off phenomenon.Under the conditions of same test with
Common PVDF is compared, and significantly improves cycle performance, and nothing drops off phenomenon after battery is disassembled.
Embodiment 6：
1g carboxymethyl chitosans and the poly- first acrylic acid of 0.5g are dissolved in 30mL water and are stirred 2 hours, after gel is uniform
Moisture is dried, is kept for 3 hours under molten state in 150 degrees Celsius of vacuum drying ovens, needed for obtaining after Temperature fall to room temperature
Lithium ion battery binding agent.
Embodiment 7：
Take 0.5g and 10mL water be dissolved in by adhesive prepared by embodiment 6, the negative material in embodiment 2 is changed to soft charcoal,
Positive electrode is changed to LiFePO4, and remaining is with embodiment with the lithium ion battery prepared with this adhesive is in 0.2C discharge and recharge bars
Under part, the reversible capacity first of half-cell reaches 230mAh/g, and full battery 10C discharge capacities are the 93% of 1C discharge capacities, and with 1C
Current charge-discharge electricity 300 times, capability retention >=94%, after battery is disassembled, nothing drops off phenomenon.Under the conditions of same test with common
PVDF is compared, and significantly improves cycle performance, and nothing drops off phenomenon after battery is disassembled.
Claims (2)
1. a kind of modified biomass Li-like ions battery adhesive, it is characterised in that sodium carboxymethylcellulose, sodium alginate, I
Primary glue, carboxymethyl chitin, the one kind and polyacrylic acid in carboxymethyl chitosan（PAA）Or polymethylacrylic acid（PMAA）Friendship
Co-product；Preparation method is the weight that natural polymer and PAA or PMAA are dissolved in water, natural polymer and PAA or PMAA
Amount is than being 1:0.1-1:Between 1, it is stirred at room temperature uniformly, after vacuum drying evaporating water, in 120-150 degree Celsius of vacuum bar
Ester bond is formed by the upper carboxyl of the hydroxyl and PAA or PMAA on natural polymer under part and is crosslinked.
2. a kind of modified biomass Li-like ions battery adhesive described in claim 1 is in various form silicon substrates and carbon-based negative
Application in the material of pole, carbon-based material include native graphite, modified natural graphite, Delanium, MCMB, carbon nanometer
Pipe, graphitized carbon fibre, hard carbon, Graphene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201310279932.XA CN103337656B (en) | 2013-07-05 | 2013-07-05 | A kind of modified biomass Li-like ions battery adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310279932.XA CN103337656B (en) | 2013-07-05 | 2013-07-05 | A kind of modified biomass Li-like ions battery adhesive |
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| Publication Number | Publication Date |
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| CN103337656A CN103337656A (en) | 2013-10-02 |
| CN103337656B true CN103337656B (en) | 2017-03-15 |
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Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327762A (en) * | 2014-09-30 | 2015-02-04 | 河南师范大学 | Enhanced-type composite adhesive of lithium ion battery, preparation method and application thereof |
| CN106159271B (en) * | 2015-04-22 | 2019-04-23 | 北京有色金属研究总院 | A kind of lithium ion battery electrode for being cross-linked in situ polymeric binder and its preparation |
| CN105576247A (en) * | 2015-12-14 | 2016-05-11 | 浙江中科立德新材料有限公司 | Modified ocean polysaccharide macromolecule lithium ion battery binder and preparing method and application thereof |
| CN105702963B (en) * | 2016-01-29 | 2018-06-29 | 长沙理工大学 | A kind of application of carboxymethyl chitosan self-crosslinking polymer in lithium ion battery silicium cathode |
| SG10201912065XA (en) * | 2016-08-30 | 2020-02-27 | Nat Univ Singapore | A battery electrode binder |
| CN107482221B (en) * | 2017-07-05 | 2019-12-24 | 长沙理工大学 | Polymer crosslinked binder and preparation method and application thereof |
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