CN109503723A - A kind of preparation method of nanometer of CMCLi - Google Patents
A kind of preparation method of nanometer of CMCLi Download PDFInfo
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- CN109503723A CN109503723A CN201811446113.9A CN201811446113A CN109503723A CN 109503723 A CN109503723 A CN 109503723A CN 201811446113 A CN201811446113 A CN 201811446113A CN 109503723 A CN109503723 A CN 109503723A
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- cmcli
- nanometer
- acid
- carboxymethyl cellulose
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 71
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 50
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 50
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 50
- 239000002253 acid Substances 0.000 claims abstract description 44
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims abstract description 37
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 32
- 239000000243 solution Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000012043 crude product Substances 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 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 21
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims abstract description 21
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000002002 slurry Substances 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 238000004140 cleaning Methods 0.000 claims abstract description 9
- 238000005342 ion exchange Methods 0.000 claims abstract description 9
- 238000005303 weighing Methods 0.000 claims abstract description 9
- 238000005119 centrifugation Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 53
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 235000019441 ethanol Nutrition 0.000 claims description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 230000020477 pH reduction Effects 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910001868 water Inorganic materials 0.000 claims description 6
- 229920000609 methyl cellulose Polymers 0.000 claims description 4
- 239000001923 methylcellulose Substances 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 19
- 229910052744 lithium Inorganic materials 0.000 abstract description 19
- 230000003647 oxidation Effects 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 3
- 238000006138 lithiation reaction Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000004513 sizing Methods 0.000 description 5
- 229960000583 acetic acid Drugs 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920003086 cellulose ether Polymers 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000005291 magnetic effect Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- 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
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
-
- 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
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The present invention relates to the preparation methods of a kind of nanometer of CMCLi in lithium battery material field.Step 1: weighing sodium carboxymethylcellulose acid is added after solvent disperses and obtain the first mixed liquor；Step 2: the first mixed liquor in step 1 being reacted, after reaction centrifugal dewatering at 30-50 DEG C, obtain crude product carboxymethyl cellulose acid；Step 3: solvent washs crude product carboxymethyl cellulose acid, centrifugation removing liquid；Lithiation step 4: dispersing carboxymethyl cellulose acid in ethanol water, and lithium hydroxide aqueous solution is added and reacts 1-4h at 20-50 DEG C；Then TEMP reagent is added to be aoxidized, step 5: reaction solution being placed in amberplex after oxidation, carries out ion-exchange detergency, cleaning solution is ethanol water, is washed after reaction solution to neutrality, by being concentrated to get a nanometer CMCLi slurries.This application provides the preparation processes of nanometer CMCLi, have prepared nanoscale carboxymethyl cellulose lithium, have improved the physical and chemical properties of carboxymethyl cellulose lithium.
Description
Technical field
The present invention relates to the technical fields of lithium battery material, more particularly, to the preparation method of a kind of nanometer of CMCLi.
Background technique
Carboxymethyl cellulose lithium salts belongs to ionic cellulose ethers, it is carboxymethyl cellulose by being acidified and corresponding alkali
Gained is neutralized, is a kind of single ion conductor, ionization can generate the anion-OCH of multiple long chains in water2COO-H2O and gold
Belong to cation, belongs to polyelectrolyte.Its aqueous solution have the effects that thickening, bonding, moisture content keep, detergent, papermaking,
Electronic component, pesticide etc. have application prospect.
Currently, commercially available carboxymethyl cellulose is all sodium carboxymethylcellulose, belongs to ionic cellulose ethers, usually pass through
Obtained from crossing alkalization, etherificate, neutralizing and wash.Sodium carboxymethylcellulose is auxiliary as a kind of novel anode material of lithium battery
Material is helped, is played the role of primarily as binder, by positive electrode, such as lithium nickel cobalt ternary material, lithium Mn-based material, phosphorus
Sour iron lithium material etc. and current-collector fit closely, and keep battery in charging and discharging capacity when high rate performance.
It is to describe a kind of preparation process of carboxymethyl cellulose lithium in CN102206286A application documents in publication No.,
It is characterized in that preparation process is divided into two parts: the preparation step 1 of (one) carboxymethyl cellulose acid: by carboxylic first made from slurry process
Base sodium cellulosate disperses in organic solvent, aqueous hydrochloric acid solution to be added, obtains mixed solution；Step 2: by the mixed liquor of step 1
It is reacted under 20 °C~50 °C, then takes off liquid, obtain crude product carboxymethyl cellulose acid；Step 3: with volumetric concentration be 80%~
The crude product carboxymethyl cellulose acid that 95% organic solvent washing step 2 obtains, the carboxymethyl cellulose acid application of high substituted degree
High levels of organic solvents washs, and then takes off liquid, drying, crushing, obtains carboxymethyl cellulose acid；(2) carboxymethyl cellulose lithium
Preparation step 1: by carboxymethyl cellulose acid obtained in (one) dispersion in organic solvent, be added LiOH*H20 aqueous solution,
Obtain mixed solution；Step 2: being neutralized to pH=6 with glacial acetic acid after the mixed liquor of (two) step 1 is reacted under 40 °C~60 °C
~8, obtain crude product carboxymethyl cellulose lithium；Step 3: the crude product carboxymethyl cellulose lithium that (two) step 2 obtains is subjected to de- liquid
Afterwards, with 75%~85% organic solvent washing of concentration, carboxymethyl cellulose with high degree lithium application high levels of organic solvents is washed
It washs；De- liquid, drying crush to obtain carboxymethyl cellulose lithium.
It is in the nature cellulose to carboxymethyl cellulose lithium obtained above, and still more in structure is macroscopically
The preparation of carboxymethyl cellulose lithium, not yet discloses the related manufacturing processes about nanometer CMCLi at present, and nanoscale material exists
Excellent performance is all had in terms of sound, light, electricity, magnetic, hot property.So nanoscale carboxymethyl can be prepared by urgently providing one kind
The method of cellulose lithium, to increase the purposes of nanometer CMCLi.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of nanometer of CMCLi, the nanoscale carboxymethyl cellulose produced
Element, the small viscosity of grain diameter are high.
Foregoing invention purpose one of the invention has the technical scheme that a nanometer preparation side of CMCLi
Method, including following preparation step:
Step 1: acidification
Step 1: weighing sodium carboxymethylcellulose acid is added after solvent disperses and obtain the first mixed liquor；
Step 2: the first mixed liquor in step 1 being reacted, after reaction centrifugal dewatering at 30-50 DEG C, obtain crude product carboxylic
Methylcellulose acid；
Step 3: solvent washs crude product carboxymethyl cellulose acid, centrifugation removing liquid；
Step 2: lithiumation
Step 4: it disperses carboxymethyl cellulose acid in ethanol water, it is added lithium hydroxide aqueous solution (concentration 1%-12%)
1-4h is reacted at 20-50 DEG C；Then TEMP reagent is added to be aoxidized；
Step 5: reaction solution being placed in amberplex after reaction, carries out ion-exchange detergency, cleaning solution is ethyl alcohol
Aqueous solution is washed after reaction solution to neutrality, by being concentrated to get a nanometer CMCLi slurries.
By using above-mentioned technical proposal, in step 1, sodium carboxymethylcellulose, which reacts after solvent disperses with acid, generates carboxylic
Methylcellulose acid, obtained crude product carboxymethyl cellulose acid obtain purer product by centrifugation abjection liquid, then
Further carboxymethyl cellulose acid, again through TEMP reagent oxidation, reacts with lithium hydroxide after oxidation after ethyl alcohol disperses and generates crude product
CMCLi, crude product CMCLi obtains CMCLi slurries after post treatment.This nanometer of CMCLi slurries compared with CMCLi optics, calorifics,
Tool improves significantly in terms of electricity, magnetics, mechanics and chemical property, using with more wide prospect of the application.
The present invention is further arranged to: at least one in solvent selection methanol, ethyl alcohol, isopropanol and acetone in step 1
At least one of kind or methanol, ethyl alcohol, isopropanol and acetone aqueous solution.
By using above-mentioned technical proposal, sodium carboxymethylcellulose powder easily disperses, and utilizes water, methanol, ethyl alcohol, isopropanol
It is at low cost with any one of acetone and combinations thereof dispersion, and the influence for reaction is smaller.
The present invention is further arranged to: any one of acid selection sulfuric acid, hydrochloric acid, acetic acid and nitric acid in rapid 1 step by step.
The present invention is further arranged to: the quality of solvent and sodium carboxymethylcellulose is 5-50:1, acid and carboxylic first in step 1
The mass ratio of base sodium cellulosate is 1-3:1.
By using above-mentioned technical proposal, the proportion selection of each component within the above range, can increase the progress of reaction
Degree.
The present invention is further arranged to: solvent selection water, ethyl alcohol or ethanol water in step 3.
By using above-mentioned technical proposal, water, ethyl alcohol or ethanol water in step 3, low in cost, using effect is good.
The present invention is further arranged to: the mass content of ethyl alcohol is greater than 65% in ethanol water in step 4.
The present invention is further arranged to: the concentration of lithium hydroxide aqueous solution is 1%-12% in step 4.
The present invention is further arranged to: the mass content of ethyl alcohol is 65-100% in ethanol water in step 5.
By using above-mentioned technical proposal, reagent is selected within the above range, and the effect of washing or dispersion is relatively good.
In conclusion advantageous effects of the invention are as follows:
1. having prepared nanoscale carboxymethyl cellulose lithium this application provides the preparation process of nanometer CMCLi, having improved carboxylic
The physical and chemical properties of methylcellulose lithium increase its scope of application；
2. nanometer CMCLi obtained in the application anode pole piece for being applied to battery is used, making for battery is further improved
Use performance.
Specific embodiment
Invention is further described in detail below.
Embodiment 1
Step 1: acidification
Step 1: weighing sodium carboxymethylcellulose 50g addition 50g sulfuric acid after the dispersion of 75wt% methanol aqueous solution and obtain the first mixing
Liquid；Wherein the mass ratio of methanol aqueous solution and sodium carboxymethylcellulose is 5:1；
Step 2: the first mixed liquor in step 1 being reacted at 30 DEG C, after reaction in 2500r/min centrifugal dewatering, is obtained
To crude product carboxymethyl cellulose acid；
Step 3: washing crude product carboxymethyl cellulose acid three times using 300ml moisture, be centrifuged removing liquid in 2500r/min；
Step 2: lithiumation
Step 4: dispersing carboxymethyl cellulose acid in 100ml ethanol water, it is water-soluble that the lithium hydroxide that concentration is 1% is added
Liquid reacts 1h at 20 DEG C；And 1ml TEMP reagent is added and is aoxidized；
Step 5: reaction solution being placed in amberplex after oxidation, carries out ion-exchange detergency, cleaning solution 300ml
Ethanol water is washed after reaction solution to neutrality, by being concentrated to get a nanometer CMCLi slurries.
The quality accounting of ethyl alcohol is 65% in ethanol water in step 4.In step 5 in ethanol water ethyl alcohol matter
Measuring content is 65%.
Embodiment 2
Step 1: acidification
Step 1: weighing sodium carboxymethylcellulose 50g 75g hydrochloric acid is added after methanol disperses and obtain the first mixed liquor；Wherein methanol
Bath raio with sodium carboxymethylcellulose is 10:1；
Step 2: the first mixed liquor in step 1 being reacted at 32 DEG C, after reaction in 2700r/min centrifugal dewatering, is obtained
To crude product carboxymethyl cellulose acid；
Step 3: washing crude product carboxymethyl cellulose acid three times using 300ml moisture, be centrifuged removing liquid in 2700r/min；
Step 2: lithiumation
Step 4: dispersing carboxymethyl cellulose acid in 100ml ethanol water, it is water-soluble that the lithium hydroxide that concentration is 3% is added
Liquid reacts 1.5h at 25 DEG C；And 5ml TEMP reagent is added and is aoxidized;
Step 5: after oxidation, reaction solution being placed in amberplex, carries out ion-exchange detergency, cleaning solution is
300ml ethanol water, is washed after reaction solution to neutrality, by being concentrated to get a nanometer CMCLi slurries.
The quality accounting of ethyl alcohol is 70% in ethanol water in step 4.In step 5 in ethanol water ethyl alcohol matter
Measuring content is 70%.
Embodiment 3
Step 1: acidification
Step 1: weighing sodium carboxymethylcellulose 50g and 125g acetic acid is added after the dispersion of 65wt% ethanol water to obtain first mixed
Close liquid；Wherein the bath raio of methanol and sodium carboxymethylcellulose is 20:1；
Step 2: the first mixed liquor in step 1 being reacted at 38 DEG C, after reaction in 2800r/min centrifugal dewatering, is obtained
To crude product carboxymethyl cellulose acid；
Step 3: washing crude product carboxymethyl cellulose acid three times using 300ml moisture, be centrifuged removing liquid in 2800r/min；
Step 2: lithiumation
Step 4: dispersing carboxymethyl cellulose acid in 120ml ethanol water, it is water-soluble that the lithium hydroxide that concentration is 5% is added
Liquid reacts 2h at 30 DEG C；And 10ml TEMP reagent is added and is aoxidized;
Step 5: after oxidation, reaction solution being placed in amberplex, carries out ion-exchange detergency, cleaning solution is
300ml ethanol water, is washed after reaction solution to neutrality, by being concentrated to get a nanometer CMCLi slurries.
The quality accounting of ethyl alcohol is 75% in ethanol water in step 4.In step 5 in ethanol water ethyl alcohol matter
Measuring content is 75%.Embodiment 4
Step 1: acidification
Step 1: weighing sodium carboxymethylcellulose 50g 150g nitric acid is added after isopropanol disperses and obtain the first mixed liquor；Wherein
The bath raio of methanol and sodium carboxymethylcellulose is 30:1；
Step 2: the first mixed liquor in step 1 being reacted at 40 DEG C, after reaction in 2800r/min centrifugal dewatering, is obtained
To crude product carboxymethyl cellulose acid；
Step 3: washing crude product carboxymethyl cellulose acid three times using 300ml moisture, be centrifuged removing liquid in 2800r/min；
Step 2: lithiumation
Step 4: dispersing carboxymethyl cellulose acid in 130ml ethanol water, it is water-soluble that the lithium hydroxide that concentration is 7% is added
Liquid reacts 3h at 40 DEG C；And 20ml TEMP reagent is added and is aoxidized;
Step 5: after oxidation, reaction solution being placed in amberplex, carries out ion-exchange detergency, cleaning solution is
300ml ethanol water, is washed after reaction solution to neutrality, by being concentrated to get a nanometer CMCLi slurries.
The quality accounting of ethyl alcohol is 75% in ethanol water in step 4.In step 5 in ethanol water ethyl alcohol matter
Measuring content is 75%.
Embodiment 5
Step 1: acidification
Step 1: weighing sodium carboxymethylcellulose 50g 150g sulfuric acid is added after acetone disperses and obtain the first mixed liquor；Wherein first
The bath raio of alcohol and sodium carboxymethylcellulose is 40:1；
Step 2: the first mixed liquor in step 1 being reacted at 45 DEG C, after reaction in 3000r/min centrifugal dewatering, is obtained
To crude product carboxymethyl cellulose acid；
Step 3: washing crude product carboxymethyl cellulose acid three times using 300ml moisture, be centrifuged removing liquid in 3000r/min；
Step 2: lithiumation
Step 4: dispersing carboxymethyl cellulose acid in 130ml ethanol water, it is water-soluble that the lithium hydroxide that concentration is 10% is added
Liquid reacts 3h at 45 DEG C；And 20ml TEMP reagent is added and is aoxidized；
Step 5: reaction solution being placed in amberplex after oxidation, carries out ion-exchange detergency, cleaning solution 300ml
Ethanol water is washed after reaction solution to neutrality, by being concentrated to get a nanometer CMCLi slurries.
The quality accounting of ethyl alcohol is 80% in ethanol water in step 4.In step 5 in ethanol water ethyl alcohol matter
Measuring content is 80%.
Embodiment 6
Step 1: acidification
Step 1: weighing sodium carboxymethylcellulose 50g and 150g acetic acid is added after the dispersion of 80wt% aqueous acetone solution to obtain first mixed
Close liquid；Wherein the bath raio of methanol and sodium carboxymethylcellulose is 50:1；
Step 2: the first mixed liquor in step 1 being reacted at 50 DEG C, after reaction in 3000r/min centrifugal dewatering, is obtained
To crude product carboxymethyl cellulose acid；
Step 3: washing crude product carboxymethyl cellulose acid three times using 300ml moisture, be centrifuged removing liquid in 3000r/min；
Step 2: lithiumation
Step 4: it disperses carboxymethyl cellulose acid in 150ml ethanol water, the lithium hydroxide water that concentration is 12% is added
Solution reacts 4h at 50 DEG C；And 20ml TEMP reagent is added and is aoxidized；
Step 5: reaction solution being placed in amberplex after oxidation, carries out ion-exchange detergency, cleaning solution 300ml
Ethanol water is washed after reaction solution to neutrality, by being concentrated to get a nanometer CMCLi slurries.
The quality accounting of ethyl alcohol is 80% in ethanol water in step 4.In step 5 in ethanol water ethyl alcohol matter
Measuring content is 80%.
Comparative example
With publication No. be CN102206286A application documents disclosed in carboxymethyl cellulose lithium preparation process as a comparison case.
The carboxymethyl cellulose lithium as made from embodiment 1-6 and comparative example all has as slurry of pole piece of positive pole binder
Purposes
Testing inspection
1, the preparation of anode sizing agent: anode sizing agent component includes following weight percentage components: 1 part of CMCLi,
LiFePO40.5 parts, LiCoO22 parts, 0.2 part of crystalline flake graphite, deionized water: 0.5 part, 0.05 part of N-Methyl pyrrolidone, it will be upper
It states component and is uniformly mixed obtained anode sizing agent.
2, it selects with a thickness of 0.016 ± 0.002mm, length X width is the pure aluminum foil of (9002) X (56.5 ± 0.2) mm, with baking
Case evaporates the solvent of the anode sizing agent after mixing, is then coated on pure aluminum foil under conditions of constant temperature is 20 °C, coated side
Density is 1.8 ± 0.020g/100cm2.
The positive maximum roll film for being coated with anode sizing agent, which is put into, is filled with nitrogen, 105 ± 5 °C of temperature, vacuum degree be-
It is toasted 10 hours in the baking oven of 0.085 ± 0.010MPaS, wherein aoxidizing in order to prevent, every 3 hours nitrogen of charge and discharge in baking oven
Gas, it is desirable that purity >=99.5% of nitrogen.
3, by after above-mentioned baking positive maximum roll film and negative maximum roll film be placed on pressure be 50~100 tons flaking machine carry out
Roller sheet, positive rolling thickness are 0.190 ± 0.002mm, carry out cut-parts after roller sheet.
Detection method:
Thermal stability: thermogravimetry test is carried out under the conditions of 300,400,500 DEG C respectively.
The testing result of 1 embodiment 1-6 of table and 1 thermal stability of comparative example
| Sample | 300 DEG C (%) | 400 DEG C (%) | 500 DEG C (%) |
| Embodiment 1 | 12 | 26 | 30 |
| Embodiment 2 | 11 | 25 | 31 |
| Embodiment 3 | 11 | 22 | 29 |
| Embodiment 4 | 9 | 22 | 29 |
| Embodiment 5 | 10 | 22 | 32 |
| Embodiment 6 | 10 | 22 | 32 |
| Comparative example | 53 | 59 | 68 |
By upper table it is found that the nanometer CMCLi in present specification is added in anode pole piece preparation, have when detecting smaller
Thermal weight loss rate, thermal stability with higher.
The embodiment of present embodiment is presently preferred embodiments of the present invention, not limits protection of the invention according to this
Range, therefore: the equivalence changes that all structures under this invention, shape, principle are done, should all be covered by protection scope of the present invention it
It is interior.
Claims (8)
1. the preparation method of a kind of nanometer of CMCLi, it is characterised in that: including following preparation step:
Step 1: acidification
Step 1: weighing sodium carboxymethylcellulose acid is added after solvent disperses and obtain the first mixed liquor；
Step 2: the first mixed liquor in step 1 being reacted, after reaction centrifugal dewatering at 30-50 DEG C, obtain crude product carboxylic
Methylcellulose acid；
Step 3: solvent washs crude product carboxymethyl cellulose acid, centrifugation removing liquid；
Step 2: lithiumation
Step 4: dispersing carboxymethyl cellulose acid in ethanol water, it is anti-at 20-50 DEG C that lithium hydroxide aqueous solution is added
Answer 1-4h；Then TEMP reagent is added to be aoxidized；
Step 5: reaction solution being placed in amberplex after oxidation reaction, carries out ion-exchange detergency, cleaning solution is
Ethanol water is washed after reaction solution to neutrality, by being concentrated to get a nanometer CMCLi slurries.
2. the preparation method of a kind of nanometer of CMCLi according to claim 1, it is characterised in that: the solvent selection in step 1
At least one of methanol, ethyl alcohol, isopropanol and acetone or at least one of methanol, ethyl alcohol, isopropanol and acetone aqueous solution.
3. the preparation method of a kind of nanometer of CMCLi according to claim 1, it is characterised in that: the acid selection sulphur in step 1
Any one of acid, hydrochloric acid, acetic acid and nitric acid.
4. the preparation method of a kind of nanometer of CMCLi according to claim 1, it is characterised in that: solvent and carboxylic first in step 1
The mass ratio of base sodium cellulosate is 5-50:1, and the sour mass ratio with sodium carboxymethylcellulose is 1-3:1.
5. the preparation method of a kind of nanometer of CMCLi according to claim 1, it is characterised in that: the solvent selection in step 3
Water, ethyl alcohol or ethanol water.
6. the preparation method of a kind of nanometer of CMCLi according to claim 1, it is characterised in that: ethanol water in step 4
The mass content of middle ethyl alcohol is greater than 65%.
7. the preparation method of a kind of nanometer of CMCLi according to claim 1, it is characterised in that: lithium hydroxide water in step 4
The concentration of solution is 1%-12%.
8. the preparation method of a kind of nanometer of CMCLi according to claim 1, it is characterised in that: ethanol water in step 5
The mass content of middle ethyl alcohol is 65-100%.
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