CN115043949A - Synthesis method of low-gel particle high-transparency carboxymethyl cellulose lithium aqueous binder - Google Patents
Synthesis method of low-gel particle high-transparency carboxymethyl cellulose lithium aqueous binder Download PDFInfo
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- CN115043949A CN115043949A CN202210882963.3A CN202210882963A CN115043949A CN 115043949 A CN115043949 A CN 115043949A CN 202210882963 A CN202210882963 A CN 202210882963A CN 115043949 A CN115043949 A CN 115043949A
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- carboxymethyl cellulose
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- 239000001768 carboxy methyl cellulose Substances 0.000 title claims abstract description 106
- 229920002134 Carboxymethyl cellulose Polymers 0.000 title claims abstract description 73
- 235000010948 carboxy methyl cellulose Nutrition 0.000 title claims abstract description 73
- 239000008112 carboxymethyl-cellulose Substances 0.000 title claims abstract description 73
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 60
- 239000011230 binding agent Substances 0.000 title claims abstract description 28
- 239000007863 gel particle Substances 0.000 title claims abstract description 25
- 238000001308 synthesis method Methods 0.000 title claims abstract description 12
- 229920002678 cellulose Polymers 0.000 claims abstract description 47
- 239000001913 cellulose Substances 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000007935 neutral effect Effects 0.000 claims abstract description 8
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 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 description 33
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 33
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 33
- 239000003960 organic solvent Substances 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229920002752 Konjac Polymers 0.000 claims description 13
- 235000010485 konjac Nutrition 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 239000012634 fragment Substances 0.000 claims description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 150000007524 organic acids Chemical class 0.000 claims description 9
- 238000006467 substitution reaction Methods 0.000 claims description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 6
- 235000019253 formic acid Nutrition 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 230000020477 pH reduction Effects 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 238000004061 bleaching Methods 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- 238000006266 etherification reaction Methods 0.000 claims description 3
- 229920005610 lignin Polymers 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 6
- 241000609240 Ambelania acida Species 0.000 claims 1
- 229920000742 Cotton Polymers 0.000 claims 1
- 239000010905 bagasse Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- 239000010902 straw Substances 0.000 claims 1
- 239000000853 adhesive Substances 0.000 description 20
- 230000001070 adhesive effect Effects 0.000 description 20
- 238000000502 dialysis Methods 0.000 description 12
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 12
- 238000002156 mixing Methods 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 230000003993 interaction Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 241001312219 Amorphophallus konjac Species 0.000 description 3
- 235000001206 Amorphophallus rivieri Nutrition 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- 239000000252 konjac Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000011856 silicon-based particle Substances 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- -1 hydrogen ions Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 241000251729 Elasmobranchii Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 238000010902 jet-milling Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/02—Alkyl or cycloalkyl ethers
- C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
- C08B11/10—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals
- C08B11/12—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals substituted with carboxylic radicals, e.g. carboxymethylcellulose [CMC]
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
- C08B1/08—Alkali cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/20—Post-etherification treatments of chemical or physical type, e.g. mixed etherification in two steps, including purification
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention discloses a synthesis method of a low-gel particle high-transparency carboxymethyl cellulose lithium aqueous binder. In the invention, the granularity of the product after reaction is in the micron order, the reaction is more uniform and stable, a neutral carboxymethyl cellulose hydrogen product is obtained by a three-in-one device, then the neutral carboxymethyl cellulose hydrogen product is added into a vertical reaction kettle, lithium ethoxide is added for stirring and reaction for 60min to 120min, and a small amount of sulfonated cellulose is added, so that the generation of gel particles can be reduced, and a low-gel-particle high-transparency carboxymethyl cellulose lithium product is obtained by the three-in-one device, and the product is in the micron order, so that the structure of a macromolecular chain is not required to be destroyed by mechanical crushing, the integrity of the molecular chain and the higher viscosity of the product are ensured, and the carboxymethyl cellulose hydrogen product is suitable for being used as a binder in lithium batteries of various types.
Description
Technical Field
The invention belongs to the technical field of adhesives, and particularly relates to a synthesis method of a low-gel particle high-transparency carboxymethyl cellulose lithium aqueous adhesive.
Background
The lithium ion battery is a high-performance secondary battery, has the advantages of high working voltage, high volume and weight energy density, long service life, low self-discharge efficiency, no memory effect, environmental friendliness and the like, and is widely applied to the fields of mobile communication equipment, notebook computers, video recorders, PDAs (personal digital assistants), digital cameras, electric tools, torpedoes, missiles and the like. In recent years, the manufacturing technology of lithium ion batteries has been greatly improved, so that the capacity of cylindrical batteries with the model number of 18650 is improved from the initial 1200mAh to 2400 mAh. However, the coating method is still used for the production method of the battery electrode sheet (positive electrode sheet and negative electrode sheet). The coating method comprises oil-phase coating and water-phase coating. At present, the oil phase coating technology is still generally adopted when the pole pieces are produced on a large scale.
Currently, the most used adhesives are fluoropolymer adhesives. However, the adhesive is not strong enough to be used conveniently.
Disclosure of Invention
The invention aims to: in order to solve the problems, the synthesis method of the low-gel particle high-transparency carboxymethyl cellulose lithium aqueous binder is provided.
The technical scheme adopted by the invention is as follows: the synthesis method of the low-gel particle high-transparency lithium carboxymethyl cellulose aqueous binder comprises the following steps:
s1, preparing cellulose, namely weighing 10-20 parts of konjak, shearing into fragments, adding the fragments into a water bath, heating to 80 ℃, and stirring until the konjak is completely dissolved;
s2, removing impurities such as lignin and the like to obtain a cellulose material after acid boiling, washing, alkali boiling, bleaching and washing, adding the cellulose material into a vertical reaction kettle (except the other kneader) to perform an alkalization reaction, and controlling the temperature to be between 0 and 20 ℃ to obtain an alkali cellulose material;
s3, reacting for 60-90 min, carrying out etherification reaction for 60-120 min by raising the temperature to 40-60 ℃, removing salt and solvent in a three-in-one device to obtain a neutral sodium carboxymethylcellulose product, and adding the neutral sodium carboxymethylcellulose product into a vertical reaction kettle;
s4, adding 100-120 parts of organic acid into the sodium carboxymethyl cellulose prepared in the step S3 for acidification reaction to generate carboxymethyl cellulose hydrogen;
s5, adding lithium ethoxide into the carboxymethyl cellulose hydrogen in the step S4, carrying out chemical reaction at the temperature of 55-65 ℃ to generate crude carboxymethyl cellulose lithium,
s6, washing with 75-85% organic solvent, washing with high-substitution carboxymethyl cellulose lithium with high-concentration organic solvent; removing liquid, drying and crushing to obtain carboxymethyl cellulose lithium;
and S7, bagging the prepared lithium carboxymethyl cellulose, and storing to finish the whole preparation process.
In a preferred embodiment, in step S6, the lithium carboxymethyl cellulose is pulverized by jet milling to obtain a product with a suitable particle size and distribution.
In a preferred embodiment, in step S4, the organic acid is one or more of oxalic acid, formic acid, succinic acid, benzoic acid, etc., so as to ensure as little damage to the polymer chains as possible, and to ensure that the generation of non-uniform gel particles and high viscosity in the product are avoided.
In a preferred embodiment, in step S4, the acid is dissolved in water or an organic solvent to form an acidified solution, and then the sodium carboxymethyl cellulose is acidified, where the mass fraction of the acidified solution is 15%, and the mass ratio of the acidified solution to the sodium carboxymethyl cellulose dry sample is 15: 1.
in a preferred embodiment, in step S6, the organic solvent is one or more of ethanol, propanol and isopropanol.
In a preferred embodiment, in the step S6, the drying temperature is controlled to be 75 degrees celsius, and the drying time is controlled to be 30 min.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
according to the invention, the citric acid is added, the complete reaction of hydroxyl functional groups of cellulose and hydrogen ions can be balanced, the granularity of the corncobs can reach micron level, the granularity of products after reaction is also in micron level, the reaction is more uniform and stable, a small amount of sulfonated cellulose is added, the generation of gel particles can be reduced, low-gel particle high-transparency carboxymethyl cellulose lithium products are obtained through three-in-one equipment, the products are in micron level, the structure of a macromolecular chain is not required to be damaged through mechanical crushing, the integrity of the molecular chain and the higher viscosity of the products are ensured, and the high-transparency carboxymethyl cellulose lithium ion binding agent is suitable for being used as a binding agent in lithium batteries of various models.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
the synthesis method of the low-gel particle high-transparency lithium carboxymethyl cellulose aqueous binder comprises the following steps:
s1, preparing cellulose, namely weighing 10 parts of konjak, cutting into fragments, and adding the fragments into 100mL of 9mol/L lithium bromide solution; heating to 80 deg.C in water bath, and stirring until rhizoma Amorphophalli is completely dissolved;
s2, transferring the dissolved konjac solution into a dialysis bag with the cut-off molecular weight of 13000, dialyzing the dialysis bag in distilled water to remove lithium bromide in the solution, and detecting bromide ions by using a silver nitrate solution to judge whether the dialysis is finished; centrifuging the cellulose solution obtained after dialysis at 6000r/min for 5min to remove impurities, and freeze-drying to obtain a cellulose solid;
s3, preparing a 2 wt% sodium carboxymethylcellulose solution for later use by using the cellulose solid prepared in the step S2, dissolving the prepared cellulose in formic acid to prepare a 2 wt% solution, mixing the cellulose solutions respectively according to 6% of the mass of the sodium carboxymethylcellulose solution, then adding sulfonated cellulose, and fully blending by using a rotation and revolution mixing and defoaming stirrer to obtain a reinforced sodium carboxymethylcellulose solution;
s4, adding 110 parts of organic acid into the sodium carboxymethyl cellulose prepared in the step S3 for acidification reaction to generate carboxymethyl cellulose hydrogen; in step S4, acid is dissolved in water or an organic solvent to form an acidified solution, and then sodium carboxymethylcellulose is acidified, where the mass fraction of the acidified solution is 15%, and the mass ratio of the acidified solution to the sodium carboxymethylcellulose dry sample is 15: 1;
s5, adding lithium ethoxide into the carboxymethyl cellulose hydrogen in the step S4, carrying out chemical reaction at the temperature of 55-65 ℃ to generate crude carboxymethyl cellulose lithium,
s6, washing with 75-85% organic solvent, washing with high-substitution carboxymethyl cellulose lithium with high-concentration organic solvent; removing liquid, drying and crushing to obtain carboxymethyl cellulose lithium; in step S6, crushing the lithium carboxymethyl cellulose by airflow crushing to obtain a product with proper particle size and distribution; in step S6, the organic solvent is one or a mixture of ethanol, propanol and isopropanol; in step S6, the drying temperature is controlled to be 75 ℃, and the drying time is controlled to be 30 min;
and S7, bagging the prepared lithium carboxymethyl cellulose, and storing to finish the whole preparation process.
In the invention, cellulose and lithium carboxymethyl cellulose are blended to prepare the sodium carboxymethyl cellulose-cellulose composite binder; the strong interaction of the binder with the active material increases the stability of the silicon during cycling, maintaining the structural integrity of the electrode. The stability of the adhesive in the using process is further improved, the mechanical property of the carboxymethyl cellulose lithium aqueous adhesive is obviously improved by adding the sulfonated cellulose, and the interaction between the adhesive and the surface of the silicon particle is enhanced. Therefore, compared with the traditional adhesive, the prepared adhesive has improved bonding firmness.
Example two:
the synthesis method of the low-gel particle high-transparency lithium carboxymethyl cellulose aqueous binder comprises the following steps:
s1, preparing cellulose, namely weighing 15 parts of konjak, cutting into fragments, and adding the fragments into 100mL of 9mol/L lithium bromide solution; heating to 80 deg.C in water bath, and stirring until rhizoma Amorphophalli is completely dissolved;
s2, transferring the dissolved konjac solution into a dialysis bag with the cut-off molecular weight of 13000, dialyzing the dialysis bag in distilled water to remove lithium bromide in the solution, and detecting bromide ions by using a silver nitrate solution to judge whether the dialysis is finished; centrifuging the cellulose solution obtained after dialysis at 6000r/min for 5min to remove impurities, and freeze-drying to obtain a cellulose solid;
s3, preparing a 2 wt% sodium carboxymethylcellulose solution for later use by using the cellulose solid prepared in the step S2, dissolving the prepared cellulose into formic acid to prepare a 2 wt% solution, mixing the cellulose solutions respectively according to 6% of the mass of the sodium carboxymethylcellulose solution, then adding sulfonated cellulose, and fully blending by using a rotation and revolution mixing and defoaming stirrer to obtain a reinforced sodium carboxymethylcellulose solution;
s4, adding 100 parts of organic acid into the sodium carboxymethyl cellulose prepared in the step S3 for acidification reaction to generate carboxymethyl cellulose hydrogen; in step S4, acid is dissolved in water or an organic solvent to form an acidified solution, and then sodium carboxymethylcellulose is acidified, where the mass fraction of the acidified solution is 15%, and the mass ratio of the acidified solution to the sodium carboxymethylcellulose dry sample is 15: 1;
s5, adding lithium ethylate into the carboxymethyl cellulose hydrogen in the step S4, carrying out chemical reaction at the temperature of 55-65 ℃ to generate crude carboxymethyl cellulose lithium,
s6, washing with 75-85% organic solvent, washing with high-substitution carboxymethyl cellulose lithium with high-concentration organic solvent; removing liquid, drying and crushing to obtain carboxymethyl cellulose lithium; in step S6, crushing the lithium carboxymethyl cellulose by airflow crushing to obtain a product with proper particle size and distribution; in step S6, the organic solvent is one or a mixture of ethanol, propanol and isopropanol; in step S6, the drying temperature is controlled to be 75 ℃, and the drying time is controlled to be 30 min;
and S7, bagging the prepared lithium carboxymethyl cellulose, and storing to finish the whole preparation process.
In the invention, cellulose and lithium carboxymethyl cellulose are blended to prepare the sodium carboxymethyl cellulose-cellulose composite binder; the strong interaction of the binder with the active material increases the stability of the silicon during cycling, maintaining the structural integrity of the electrode. The stability of the adhesive in the using process is further improved, the mechanical property of the carboxymethyl cellulose lithium aqueous adhesive is obviously improved by adding the sulfonated cellulose, and the interaction between the adhesive and the surface of the silicon particle is enhanced. Therefore, compared with the traditional adhesive, the prepared adhesive has improved bonding firmness.
Example three:
the synthesis method of the low-gel particle high-transparency lithium carboxymethyl cellulose aqueous binder comprises the following steps:
s1, preparing cellulose, namely weighing 15 parts of konjak, cutting into fragments, and adding the fragments into 100mL of 9mol/L lithium bromide solution; heating to 80 deg.C in water bath, and stirring until rhizoma Amorphophalli is completely dissolved;
s2, transferring the dissolved konjac solution into a dialysis bag with the cut-off molecular weight of 13000, dialyzing the dialysis bag in distilled water to remove lithium bromide in the solution, and detecting bromide ions by using a silver nitrate solution to judge whether the dialysis is finished; centrifuging the cellulose solution obtained after dialysis at 6000r/min for 5min to remove impurities, and freeze-drying to obtain a cellulose solid;
s3, preparing a 2 wt% sodium carboxymethylcellulose solution for later use by using the cellulose solid prepared in the step S2, dissolving 15 parts of prepared cellulose in formic acid to prepare a 2 wt% solution, mixing the cellulose solutions respectively according to 6% of the mass of the sodium carboxymethylcellulose solution, then adding sulfonated cellulose, and fully blending by using a rotation-revolution mixing and defoaming stirrer to obtain a reinforced sodium carboxymethylcellulose solution;
s4, adding 120 parts of organic acid into the sodium carboxymethyl cellulose prepared in the step S3 to carry out acidification reaction to generate carboxymethyl cellulose hydrogen; in step S4, acid is dissolved in water or an organic solvent to form an acidified solution, and then sodium carboxymethylcellulose is acidified, where the mass fraction of the acidified solution is 15%, and the mass ratio of the acidified solution to the sodium carboxymethylcellulose dry sample is 15: 1;
s5, adding lithium ethoxide into the carboxymethyl cellulose hydrogen in the step S4, carrying out chemical reaction at the temperature of 55-65 ℃ to generate crude carboxymethyl cellulose lithium,
s6, washing with 75-85% organic solvent, washing with high-substitution carboxymethyl cellulose lithium with high-concentration organic solvent; removing liquid, drying and crushing to obtain carboxymethyl cellulose lithium; in step S6, crushing the lithium carboxymethyl cellulose by airflow crushing to obtain a product with proper particle size and distribution; in step S6, the organic solvent is one or a mixture of ethanol, propanol and isopropanol; in step S6, the drying temperature is controlled to be 75 ℃, and the drying time is controlled to be 30 min;
and S7, bagging the prepared lithium carboxymethyl cellulose, and storing to finish the whole preparation process.
In the invention, cellulose and lithium carboxymethyl cellulose are blended to prepare the sodium carboxymethyl cellulose-cellulose composite binder; the strong interaction of the binder with the active material increases the stability of the silicon during cycling, maintaining the structural integrity of the electrode. The stability of the adhesive in the using process is further improved, the mechanical property of the carboxymethyl cellulose lithium aqueous adhesive is obviously improved by adding the sulfonated cellulose, and the interaction between the adhesive and the surface of the silicon particle is enhanced. Therefore, compared with the traditional adhesive, the prepared adhesive has improved bonding firmness.
Example four:
the synthesis method of the low-gel particle high-transparency lithium carboxymethyl cellulose aqueous binder comprises the following steps:
s1, preparing cellulose, namely weighing 10-20 parts of konjak, cutting into fragments, adding the fragments into a water bath, heating to 80 ℃, and stirring until the konjak is completely dissolved;
s2, removing impurities such as lignin and the like to obtain a cellulose material after acid boiling, washing, alkali boiling, bleaching and washing, adding the cellulose material into a vertical reaction kettle (except the other kneader) to perform an alkalization reaction, and controlling the temperature to be between 0 and 20 ℃ to obtain an alkali cellulose material;
s3, reacting for 60-90 min, carrying out etherification reaction for 60-120 min by raising the temperature to 40-60 ℃, removing salt and solvent in a three-in-one device to obtain a neutral sodium carboxymethylcellulose product, and adding the neutral sodium carboxymethylcellulose product into a vertical reaction kettle;
s4, adding 100-120 parts of organic acid into the sodium carboxymethyl cellulose prepared in the step S3 for acidification reaction to generate carboxymethyl cellulose hydrogen;
s5, adding lithium ethylate into the carboxymethyl cellulose hydrogen in the step S4, carrying out chemical reaction at the temperature of 55-65 ℃ to generate crude carboxymethyl cellulose lithium,
s6, washing with 75-85% organic solvent, washing with high-substitution carboxymethyl cellulose lithium with high-concentration organic solvent; removing liquid, drying and crushing to obtain carboxymethyl cellulose lithium;
and S7, bagging the prepared lithium carboxymethyl cellulose, and storing to finish the whole preparation process.
In step S6, the lithium carboxymethyl cellulose is pulverized by airflow pulverization to obtain a product with a suitable particle size and distribution.
In the step S4, the organic acid is one or more of oxalic acid, formic acid, succinic acid, benzoic acid, etc.
In the step S4, acid is dissolved in water or an organic solvent to form an acidified solution, and then sodium carboxymethylcellulose is acidified, where the mass fraction of the acidified solution is 15%, and the mass ratio of the acidified solution to the sodium carboxymethylcellulose dry sample is 15: 1.
in the step S6, the organic solvent is one or a mixture of ethanol, propanol and isopropanol.
In the step S6, the drying temperature is controlled to be 75 ℃, the drying time is controlled to be 30min, citric acid is added to balance the complete reaction of hydroxyl functional groups of cellulose and hydrogen ions, the granularity of the corncobs can reach micron level, the granularity of products after reaction is also at micron level, the reaction is more uniform and stable, a small amount of sulfonated cellulose is added, the generation of gel particles can be reduced, low-gel particle high-transparency carboxymethyl cellulose lithium products are obtained through three-in-one equipment, the products are at micron level, the structure of a macromolecular chain is not damaged through mechanical crushing, the completeness of the molecular chain and the viscosity of the products are guaranteed, and the binder is suitable for being used as a binder in lithium batteries of various types.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (7)
1. The synthesis method of the low-gel particle high-transparency carboxymethyl cellulose lithium aqueous binder is characterized by comprising the following steps of: the synthesis method of the low-gel particle high-transparency carboxymethyl cellulose lithium aqueous binder comprises the following steps:
s1, preparing cellulose, namely weighing 10-20 parts of konjak, cutting into fragments, adding the fragments into a water bath, heating to 80 ℃, and stirring until the konjak is completely dissolved;
s2, removing impurities such as lignin and the like to obtain a cellulose material after acid boiling, washing, alkali boiling, bleaching and washing, adding the cellulose material into a vertical reaction kettle (except the other kneader) to perform an alkalization reaction, and controlling the temperature to be between 0 and 20 ℃ to obtain an alkali cellulose material;
s3, reacting for 60-90 min, carrying out etherification reaction for 60-120 min by raising the temperature to 40-60 ℃, removing salt and solvent in a three-in-one device to obtain a neutral sodium carboxymethylcellulose product, and adding the neutral sodium carboxymethylcellulose product into a vertical reaction kettle;
s4, adding 100-120 parts of organic acid into the sodium carboxymethyl cellulose prepared in the step S3 for acidification reaction to generate carboxymethyl cellulose hydrogen;
s5, adding lithium ethoxide into the carboxymethyl cellulose hydrogen in the step S4, carrying out chemical reaction at the temperature of 55-65 ℃ to generate crude carboxymethyl cellulose lithium,
s6, washing with 75-85% organic solvent, washing with high-substitution carboxymethyl cellulose lithium with high-concentration organic solvent; removing liquid, drying and crushing to obtain carboxymethyl cellulose lithium;
and S7, bagging the prepared lithium carboxymethyl cellulose, and storing to finish the whole preparation process.
2. The method for synthesizing the low-gel particle high-transparency lithium carboxymethyl cellulose aqueous binder according to claim 1, wherein: in step S6, the lithium carboxymethyl cellulose is pulverized by airflow pulverization to obtain a product with a suitable particle size and distribution.
3. The method for synthesizing the low-gel particle high-transparency lithium carboxymethyl cellulose aqueous binder according to claim 1, wherein: in the step S4, the organic acid is one or more of oxalic acid, formic acid, succinic acid, benzoic acid, etc.
4. The method for synthesizing the low-gel particle high-transparency lithium carboxymethyl cellulose aqueous binder according to claim 1, wherein: in the step S4, acid is dissolved in water or an organic solvent to form an acidified solution, and then sodium carboxymethylcellulose is acidified, where the mass fraction of the acidified solution is 15%, and the mass ratio of the acidified solution to the sodium carboxymethylcellulose dry sample is 15: 1.
5. the method for synthesizing the low-gel particle high-transparency lithium carboxymethyl cellulose aqueous binder according to claim 1, wherein: in the step S6, the organic solvent is one or a mixture of ethanol, propanol and isopropanol.
6. The method for synthesizing the low-gel particle high-transparency lithium carboxymethyl cellulose aqueous binder according to claim 1, wherein: in the step S6, the drying temperature is controlled to be 75 ℃, and the drying time is controlled to be 30 min.
7. The method for synthesizing the low-gel particle high-transparency lithium carboxymethyl cellulose aqueous binder according to claim 1, wherein: the production raw materials are one or more of konjak, bagasse, straws, cotton or corncobs and the like.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115521382A (en) * | 2022-10-19 | 2022-12-27 | 向能新型材料科技(河北)有限公司 | Preparation method of sodium carboxymethylcellulose by high-purity bath slurry method |
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| JP2000082472A (en) * | 1998-09-03 | 2000-03-21 | Dai Ichi Kogyo Seiyaku Co Ltd | Nonaqueous battery electrode |
| CN102167749A (en) * | 2011-02-22 | 2011-08-31 | 广西大学 | Method for preparing high-substitution and high-viscosity sodium carboxymethyl cellulose from bagasse |
| CN113912742A (en) * | 2021-09-07 | 2022-01-11 | 重庆理工大学 | Synthesis method of lithium carboxymethyl cellulose with ultrahigh substitution degree and ultrahigh viscosity |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2000082472A (en) * | 1998-09-03 | 2000-03-21 | Dai Ichi Kogyo Seiyaku Co Ltd | Nonaqueous battery electrode |
| CN102167749A (en) * | 2011-02-22 | 2011-08-31 | 广西大学 | Method for preparing high-substitution and high-viscosity sodium carboxymethyl cellulose from bagasse |
| CN113912742A (en) * | 2021-09-07 | 2022-01-11 | 重庆理工大学 | Synthesis method of lithium carboxymethyl cellulose with ultrahigh substitution degree and ultrahigh viscosity |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115521382A (en) * | 2022-10-19 | 2022-12-27 | 向能新型材料科技(河北)有限公司 | Preparation method of sodium carboxymethylcellulose by high-purity bath slurry method |
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