CN115215945A - Lithium carboxymethyl cellulose and preparation method thereof - Google Patents
Lithium carboxymethyl cellulose and preparation method thereof Download PDFInfo
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- CN115215945A CN115215945A CN202210946298.XA CN202210946298A CN115215945A CN 115215945 A CN115215945 A CN 115215945A CN 202210946298 A CN202210946298 A CN 202210946298A CN 115215945 A CN115215945 A CN 115215945A
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- 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]
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Abstract
The invention relates to the technical field of lithium carboxymethyl cellulose, in particular to lithium carboxymethyl cellulose and a preparation method thereof. The preparation method of the lithium carboxymethyl cellulose comprises the following steps: the sodium carboxymethyl cellulose solution and the weak acid solution react under 2-50MPa, and/or the hydrogen carboxymethyl cellulose solution and the lithium hydroxide solution react under 2-50 MPa. The carboxymethyl cellulose lithium prepared by the invention has high purity and low impurity content.
Description
Technical Field
The invention relates to the technical field of lithium carboxymethyl cellulose, in particular to lithium carboxymethyl cellulose and a preparation method thereof.
Background
The lithium ion battery has the characteristics of high working voltage, high energy density, long cycle life and the like, and is widely applied to the fields of consumer electronics, electric automobiles, energy storage power stations and the like. At present, a negative electrode plate of a lithium ion battery is prepared by coating graphite, a conductive agent, a binder and a solvent on copper foil after preparing slurry. According to different solvents, the slurry is divided into an oily system and an aqueous system; the oily system adhesive is polyvinylidene fluoride (PVDF), the solvent is N-methyl pyrrolidone (NMP), and the organic system has the defects of high material cost, toxicity of NMP, chemical reaction between lithium and PVDF in the heating process of the prepared battery and the like, so the organic system is gradually eliminated by a water-based system.
The binder in the aqueous system is mainly sodium carboxymethylcellulose and styrene butadiene rubber emulsion which are matched for use. The sodium carboxymethyl cellulose is used as an aqueous thickening agent, disperses a negative electrode active material and a conductive agent, assists in binding the negative electrode active material and a current collector, and plays a thickening role to prevent the negative electrode slurry from settling; the styrene-butadiene rubber emulsion plays a role in bonding.
In recent years, carboxymethyl cellulose lithium is applied to an aqueous system in small batches, and compared with sodium carboxymethyl cellulose, carboxymethyl cellulose lithium as a thickening agent can effectively increase the number of freely moving lithium ions in a negative electrode plate, reduce the diffusion distance from the lithium ions to the surface of a negative electrode graphite material, and improve the charge-discharge efficiency of the graphite material, so that the rate charge-discharge performance and the cycle life of a lithium ion battery are improved, and more people pay more attention.
There are currently two methods of preparing lithium carboxymethyl cellulose: one-step and two-step processes. The one-step method is to adopt carboxymethyl cellulose lithium prepared by the traditional preparation process of sodium carboxymethyl cellulose, namely, the preparation method is prepared by the working procedures of alkalization, etherification, washing, drying, crushing and the like. This method has the following disadvantages: firstly, the alkalinity and the solubility of LiOH are far less than those of NaOH, cellulose is not uniformly contacted with alkali liquor in the alkalization process, the alkalization is incomplete, the substitution degree is low, and the dissolving capacity is poor; excessive free alkali, low utilization rate of etherifying agent in the etherification process, increased by-products and low purity of finished products. And the price of LiOH is high, and the LiOH is used for alkalizing cellulose, so that the cost is increased sharply.
The two-step method is to add a certain mass fraction of strong acid into an ethanol solution of sodium carboxymethylcellulose for acidification to prepare carboxymethyl cellulose hydrogen, and then add lithium hydroxide to prepare the carboxymethyl cellulose lithium. The method has the defects that: in industrial production, strong acid inevitably causes great corrosion to various iron containers, the iron content of the product is increased, and the larger the iron content is, the larger the self-discharge of the battery is.
Disclosure of Invention
The invention provides lithium carboxymethyl cellulose and a preparation method thereof, which are used for overcoming the defect of high impurity content of lithium carboxymethyl cellulose in the prior art and realizing the preparation of high-purity lithium carboxymethyl cellulose.
The invention provides a preparation method of carboxymethyl cellulose hydrogen (CMC-H), which comprises the following steps: the sodium carboxymethyl cellulose solution reacts with the weak acid solution under 2-50MPa to prepare the carboxymethyl cellulose hydrogen. According to the invention, the carboxymethyl cellulose hydrogen is prepared by acidifying the sodium carboxymethyl cellulose with the weak acid under high pressure, so that the risk of introducing metal impurities by strong acid acidification is overcome, and meanwhile, compared with a normal-temperature environment, the acidification degree is promoted under the high-pressure environment, so that the high-purity carboxymethyl cellulose hydrogen is prepared.
In some embodiments, the sodium carboxymethyl cellulose solution is reacted with the weak acid solution at 12 to 25 MPa.
According to the preparation method of carboxymethyl cellulose hydrogen provided by the invention, the weak acid in the weak acid solution is any one of acetic acid, oxalic acid, formic acid and nitrous acid.
And/or the mass fraction of the weak acid solution is 5-40%, preferably 8-30%.
According to the preparation method of the carboxymethyl cellulose hydrogen provided by the invention, the sodium carboxymethyl cellulose solution and the weak acid solution react for 1-5h, preferably 1.5-3h. The invention shortens the time of acidification reaction and can improve the purity of carboxymethyl cellulose hydrogen.
And/or the reaction temperature of the sodium carboxymethyl cellulose solution and the weak acid solution is 20-50 ℃, preferably 25-45 ℃.
According to the preparation method of the carboxymethyl cellulose hydrogen provided by the invention, the mass ratio of the sodium carboxymethyl cellulose to the solvent in the sodium carboxymethyl cellulose solution is 8-15.
Preferably, the solvent is one or more of water, ethanol, isopropanol, tert-butanol and acetone.
According to the preparation method of the carboxymethyl cellulose hydrogen provided by the invention, the mass ratio of the sodium carboxymethyl cellulose solution to the weak acid solution is 0.2-2: 1.
The invention also provides carboxymethyl cellulose hydrogen, which is prepared by any one of the preparation methods of carboxymethyl cellulose hydrogen.
The invention also provides a preparation method of the lithium carboxymethyl cellulose, which comprises any one of the preparation methods of the hydrogen carboxymethyl cellulose.
And/or, reacting the carboxymethyl cellulose hydrogen solution with the lithium hydroxide solution under 2-50 MPa. The invention adopts weak acid to acidify under high pressure and lithiate under high pressure, and the prepared carboxymethyl cellulose lithium material has high lithium content and low sodium impurity and iron impurity content.
In some embodiments, the carboxymethyl cellulose hydrogen solution is reacted with the lithium hydroxide solution at 12 to 25 MPa.
In some embodiments, the carboxymethyl cellulose sodium solution and the carboxymethyl cellulose hydrogen solution prepared from the weak acid solution are dehydrated and washed to prepare carboxymethyl cellulose hydrogen solid, the carboxymethyl cellulose hydrogen solid is dissolved by a solvent to obtain a carboxymethyl cellulose hydrogen solution, and the obtained carboxymethyl cellulose hydrogen solution is reacted with a lithium hydroxide solution to prepare the lithium carboxymethyl cellulose.
According to the preparation method of the lithium carboxymethyl cellulose provided by the invention, in a reaction system of a carboxymethyl cellulose hydrogen solution and a lithium hydroxide solution, the molar ratio of the lithium hydroxide to the carboxymethyl cellulose hydrogen is (1.5-3): 1; preferably, the molar ratio of lithium hydroxide to carboxymethyl cellulose hydrogen is 2:1.
and/or the reaction time of the carboxymethyl cellulose hydrogen solution and the lithium hydroxide solution is 1 to 5 hours, preferably 1.5 to 3 hours.
And/or the reaction temperature of the carboxymethyl cellulose hydrogen solution and the lithium hydroxide solution is 20-50 ℃, preferably 20-40 ℃.
According to the preparation method of the lithium carboxymethyl cellulose, provided by the invention, the pH value of a substance obtained by reacting a hydrogen carboxymethyl cellulose solution with a lithium hydroxide solution is adjusted to 6-8 to obtain a crude lithium carboxymethyl cellulose, and the crude lithium carboxymethyl cellulose is washed, subjected to liquid removal and dried to obtain the lithium carboxymethyl cellulose.
In some embodiments, the method for preparing lithium carboxymethyl cellulose comprises the following steps:
1. weighing a certain mass of sodium carboxymethylcellulose, dissolving and dispersing in a solvent (the solvent is one or more of water, ethanol, isopropanol, tert-butyl alcohol and acetone), wherein the mass ratio of the sodium carboxymethylcellulose to the solvent is 8-15;
2. placing the solution prepared in the step 1 into a 100L high-pressure kettle, adding a weak acid solution (the weak acid can be one of acetic acid, oxalic acid and oxalic acid, and the mass fraction of the weak acid solution is 5-40%) with the mass fraction of 10-30%, then sealing the high-pressure kettle, pressurizing the high-pressure kettle at the pressure of 2-50MPa for 1-5h, and carrying out an acidification reaction at the reaction temperature of 20-50 ℃; after the reaction is finished, dehydrating to obtain crude carboxymethyl cellulose hydrogen;
the mass ratio of the weak acid solution to the sodium carboxymethyl cellulose is 0.2-2: 1.
3. Washing the carboxymethyl cellulose hydrogen crude product obtained in the step 2 by using 30-100% of ethanol in percentage by mass, and then removing liquid, drying and crushing to obtain high-purity carboxymethyl cellulose acid hydrogen;
4. in a 100L autoclave, dispersing carboxymethylcellulose acid hydrogen in an ethanol aqueous solution (the mass ratio of the carboxymethylcellulose acid hydrogen to the ethanol aqueous solution is 8-15, adding a lithium hydroxide aqueous solution with the mass fraction of 3-15%, pressurizing at the pressure of 2-50MPa for 1-5h, and controlling the temperature at 20-50 ℃; the molar ratio of the lithium hydroxide to the carboxymethyl cellulose hydrogen is 2:1.
5. neutralizing the reacted substance in the step 4 with glacial acetic acid until the pH value is 6-8 to obtain a crude product of the lithium carboxymethyl cellulose; after liquid removal, washing the mixture by using 30 to 100 percent ethanol, removing the liquid, drying and crushing the mixture to obtain the lithium carboxymethyl cellulose.
In some embodiments, the method for preparing lithium carboxymethyl cellulose comprises: the solution of acetic acid or oxalic acid reacts with the sodium carboxymethyl cellulose solution at the temperature of 28-42 ℃ for 1.5-3.5h under the pressure of 12-25MPa to prepare carboxymethyl cellulose hydrogen, and the carboxymethyl cellulose hydrogen solution reacts with the lithium hydroxide solution at the temperature of 32-40 ℃ for 1.5-2.5h to prepare carboxymethyl cellulose lithium. Under the conditions, the prepared carboxymethyl cellulose lithium has fewer metal impurities and higher purity.
The invention also provides lithium carboxymethyl cellulose, which is prepared by any one of the preparation methods of the lithium carboxymethyl cellulose.
The use of any of the above methods for the preparation of hydrogen from carboxymethylcellulose or any of the above methods for the preparation of lithium from carboxymethylcellulose for increasing the purity of lithium from carboxymethylcellulose or for reducing impurities from lithium from carboxymethylcellulose.
The invention has the beneficial effects that:
(1) The invention provides a novel preparation method of carboxymethyl cellulose hydrogen, which can improve the purity of the carboxymethyl cellulose hydrogen by carrying out acidification reaction under high pressure by using weak acid.
(2) According to the invention, the sodium carboxymethylcellulose is acidified by weak acid under high pressure to prepare the lithium carboxymethylcellulose, so that the risk of introducing metal impurities by strong acid acidification is overcome, and meanwhile, compared with a normal-temperature environment, the acidification degree is promoted under high pressure, and the high-purity lithium carboxymethylcellulose is prepared.
Detailed Description
To make the objects, technical solutions and advantages of the present invention clearer and more complete, the technical solutions of the present invention will be described below clearly, and it is obvious that the described embodiments are some, not all embodiments of the present invention. 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.
Example 1
1. Selecting sodium carboxymethylcellulose with a degree of substitution DS of 0.86 and a purity of 99.98% from Henweiyi science and technology Limited;
2. weighing 3026g of sodium carboxymethylcellulose, dissolving and dispersing in a solvent (the solvent is an isopropanol solution with the mass fraction of 90%), wherein the mass ratio of the sodium carboxymethylcellulose to the solvent is 12;
3. placing the solution prepared in the step 1 in a 100L high-pressure kettle, adding 1245g of acetic acid solution with the mass fraction of 20%, sealing the high-pressure kettle, and pressurizing under 15MPa to perform an acidification reaction (the reaction temperature is 35 ℃ and the reaction time is 3 h); after the reaction is finished, dehydrating to obtain crude carboxymethyl cellulose hydrogen;
4. washing the crude product of carboxymethyl cellulose hydrogen obtained in the step 3 by using an ethanol solution with the mass fraction of 80%, and then removing liquid, drying and crushing to obtain high-purity carboxymethyl cellulose acid hydrogen;
5. in a 100L autoclave, 3700g of carboxymethyl cellulose acid hydrogen is dispersed in ethanol water solution, the mass ratio of the carboxymethyl cellulose acid hydrogen to the ethanol water solution is 13;
6. neutralizing the substance obtained after the reaction in the step 5 by using glacial acetic acid until the pH value is 6.9 to obtain a crude product of the lithium carboxymethyl cellulose; after liquid removal, washing the mixture by using an ethanol solution with the mass fraction of 80%, removing the liquid, drying and crushing to obtain the lithium carboxymethyl cellulose.
Example 2
1. Selecting sodium carboxymethylcellulose with a degree of substitution DS of 0.93 and a purity of 99.97% from the Hederai Weiyi science and technology Limited company;
2. weighing 3200g of sodium carboxymethylcellulose, dissolving and dispersing in a solvent, wherein the mass ratio of the sodium carboxymethylcellulose to the solvent is 13; the solvent is 90% ethanol solution by mass;
3. placing the solution prepared in the step 1 into a 100L high-pressure kettle, adding 3920g of acetic acid solution with the mass fraction of 10%, sealing the high-pressure kettle, and carrying out acidification reaction under the pressure of 20MPa (the reaction temperature is 30 ℃ and the reaction time is 2 h); after the reaction is finished, dehydrating to obtain crude carboxymethyl cellulose hydrogen;
4. washing the crude product of carboxymethyl cellulose hydrogen obtained in the step 3 by using an ethanol solution with the mass fraction of 80%, and then removing liquid, drying and crushing to obtain high-purity carboxymethyl cellulose acid hydrogen;
5. in a 100L autoclave, 2950g of carboxymethyl cellulose acid hydrogen is dispersed in an ethanol water solution, the mass ratio of the carboxymethyl cellulose acid hydrogen to the ethanol water solution is 13;
6. neutralizing the substance obtained after the reaction in the step 5 by using glacial acetic acid until the pH value is 7.1 to obtain a crude product of the lithium carboxymethyl cellulose; after liquid removal, washing the mixture by using an ethanol solution with the mass fraction of 80%, removing the liquid, drying and crushing the mixture to obtain the lithium carboxymethyl cellulose.
Example 3
1. Selecting sodium carboxymethylcellulose with the degree of substitution DS of 1.05 and the purity of 99.97 percent from the Hederai Weiyi science and technology Limited company;
2. weighing 3500g of sodium carboxymethylcellulose, dissolving and dispersing in a solvent, wherein the mass ratio of the sodium carboxymethylcellulose to the solvent is 13; the solvent is 90% ethanol solution by mass;
3. placing the solution prepared in the step 1 in a 100L high-pressure autoclave, adding 836g of oxalic acid solution with the mass fraction of 10%, sealing the high-pressure autoclave, and pressurizing under the pressure of 18MPa to perform acidification reaction (the reaction temperature is 40 ℃ and the reaction time is 2 hours); after the reaction is finished, dehydrating to obtain crude carboxymethyl cellulose hydrogen;
4. washing the crude product of carboxymethyl cellulose hydrogen obtained in the step 3 by using an ethanol solution with the mass fraction of 80%, and then removing liquid, drying and crushing to obtain high-purity carboxymethyl cellulose acid hydrogen;
5. in a 100L autoclave, 4100g of carboxymethyl cellulose acid hydrogen is dispersed in ethanol water solution, the mass ratio of the carboxymethyl cellulose acid hydrogen to the ethanol water solution is 14;
6. neutralizing the substance obtained after the reaction in the step 5 by using glacial acetic acid until the pH value is 7.2 to obtain crude product lithium carboxymethyl cellulose; after liquid removal, washing the mixture by using an ethanol solution with the mass fraction of 80%, removing the liquid, drying and crushing the mixture to obtain the lithium carboxymethyl cellulose.
Comparative example 1
Compared to example 1:
the reactions of step 3 and step 5 are all carried out under normal pressure, and the rest is unchanged.
Comparative example 2
Compared to comparative example 1:
and (3) replacing the acetic acid in the step (3) with hydrochloric acid, and keeping the rest unchanged.
Examples of the experiments
The purity of lithium carboxymethyl cellulose prepared in examples 1 to 3 and comparative examples 1 to 2 was measured.
The purity detection method comprises the following steps: detecting the content of lithium chloride and lithium glycolate according to the ASTM D1439-03 standard, and obtaining the lithium chloride and lithium glycolate by a subtraction method;
| purity/%) | Iron content (ppm) | |
| Example 1 | 99.63 | 12 |
| Example 2 | 99.69 | 16 |
| Example 3 | 99.73 | 13 |
| Comparative example 1 | 85.57 | 6 |
| Comparative example 2 | 95.31 | 122 |
As can be seen from the examples and comparative examples of the present invention, the purity of lithium carboxymethyl cellulose can be greatly improved and the iron content in lithium carboxymethyl cellulose can be reduced by using the method of the present invention.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, and 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 (10)
1. The preparation method of carboxymethyl cellulose hydrogen is characterized by comprising the following steps: the sodium carboxymethyl cellulose solution reacts with the weak acid solution under the pressure of 2-50MPa to prepare the carboxymethyl cellulose hydrogen.
2. The method for producing carboxymethyl cellulose hydrogen according to claim 1, wherein the weak acid in the weak acid solution is any one of acetic acid, oxalic acid, formic acid, and nitrous acid;
and/or the mass fraction of the weak acid solution is 5% -40%.
3. The method for preparing carboxymethyl cellulose hydrogen according to claim 1 or 2, wherein the sodium carboxymethyl cellulose solution is reacted with the weak acid solution for 1 to 5 hours;
and/or the reaction temperature of the sodium carboxymethyl cellulose solution and the weak acid solution is 20-50 ℃.
4. The method for preparing carboxymethyl cellulose hydrogen according to any one of claims 1 to 3, wherein the mass ratio of the sodium carboxymethyl cellulose to the solvent in the sodium carboxymethyl cellulose solution is 8 to 15.
5. The method for preparing hydrogen carboxymethylcellulose according to any one of claims 1-4, wherein the mass ratio of the sodium carboxymethylcellulose solution to the weak acid solution is 0.2-2: 1.
6. A method for producing lithium carboxymethyl cellulose, comprising the method for producing hydrogen carboxymethyl cellulose according to any one of claims 1 to 5;
and/or, reacting the carboxymethyl cellulose hydrogen solution with the lithium hydroxide solution under 2-50 MPa.
7. The method for preparing lithium carboxymethyl cellulose according to claim 6, wherein in the reaction system of the solution of carboxymethyl cellulose and the solution of lithium hydroxide, the molar ratio of lithium hydroxide to carboxymethyl cellulose hydrogen is 1.5 to 3:1;
and/or the reaction time of the carboxymethyl cellulose hydrogen solution and the lithium hydroxide solution is 1-5h;
and/or the reaction temperature of the carboxymethyl cellulose hydrogen solution and the lithium hydroxide solution is 20-50 ℃.
8. The preparation method of lithium carboxymethyl cellulose according to claim 6 or 7, characterized in that a substance obtained by reacting a hydrogen carboxymethyl cellulose solution with a lithium hydroxide solution is adjusted to pH 6-8 to obtain crude lithium carboxymethyl cellulose, and the crude lithium carboxymethyl cellulose is washed, dehydrated and dried after dehydration to obtain lithium carboxymethyl cellulose.
9. Lithium carboxymethyl cellulose produced by the method for producing lithium carboxymethyl cellulose according to any one of claims 6 to 8.
10. Use of a process for the preparation of carboxymethyl cellulose hydrogen according to any one of claims 1 to 5 or of a process for the preparation of lithium carboxymethyl cellulose according to any one of claims 6 to 8 for increasing the purity of lithium carboxymethyl cellulose or for reducing lithium carboxymethyl cellulose impurities.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206286A (en) * | 2011-05-16 | 2011-10-05 | 北京理工大学 | Preparation method of lithium carboxymethyl cellulose for lithium battery |
| CN105330751A (en) * | 2015-11-05 | 2016-02-17 | 重庆力宏精细化工有限公司 | Continuous production method of carboxymethylcellulose lithium for lithium batteries |
| CN106366203A (en) * | 2016-08-31 | 2017-02-01 | 泸州北方化学工业有限公司 | Preparation method of low sodium salt carboxymethyl cellulose lithium |
| CN112724266A (en) * | 2020-12-28 | 2021-04-30 | 常熟威怡科技有限公司 | Preparation method of lithium carboxymethyl cellulose for lithium battery |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206286A (en) * | 2011-05-16 | 2011-10-05 | 北京理工大学 | Preparation method of lithium carboxymethyl cellulose for lithium battery |
| CN105330751A (en) * | 2015-11-05 | 2016-02-17 | 重庆力宏精细化工有限公司 | Continuous production method of carboxymethylcellulose lithium for lithium batteries |
| CN106366203A (en) * | 2016-08-31 | 2017-02-01 | 泸州北方化学工业有限公司 | Preparation method of low sodium salt carboxymethyl cellulose lithium |
| CN112724266A (en) * | 2020-12-28 | 2021-04-30 | 常熟威怡科技有限公司 | Preparation method of lithium carboxymethyl cellulose for lithium battery |
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