CN105330751A - Continuous production method of carboxymethylcellulose lithium for lithium batteries - Google Patents
Continuous production method of carboxymethylcellulose lithium for lithium batteries Download PDFInfo
- Publication number
- CN105330751A CN105330751A CN201510742242.2A CN201510742242A CN105330751A CN 105330751 A CN105330751 A CN 105330751A CN 201510742242 A CN201510742242 A CN 201510742242A CN 105330751 A CN105330751 A CN 105330751A
- Authority
- CN
- China
- Prior art keywords
- lithium
- carboxymethyl cellulose
- cmc
- production method
- continuous production
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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]
Abstract
The invention discloses a continuous production method of carboxymethylcellulose lithium for lithium batteries in order to solve the problems that a lithium ion battery adhesion agent pollutes the environment, is single in function and high in price. The production method includes the steps that sodium carboxymethyl cellulose is prepared, and the carboxymethylcellulose lithium is obtained after the sodium carboxymethyl cellulose is acidized, alkalinized and purified. The prepared carboxymethylcellulose lithium breaks the pattern that autonomous mass production of carboxymethylcellulose lithium cannot be achieved domestically, according to the current condition of domestic production, on the basis that the performance of the carboxymethylcellulose lithium is guaranteed, continuous and large-batch production of the carboxymethylcellulose lithium can be achieved, and production cost is greatly reduced. A series of product performance testing preparation parameters are summarized in the method, and the parameters are quality control indexes of carboxymethylcellulose lithium and can also provide a reference for establishing standards of industrialized carboxymethylcellulose lithium in future.
Description
Technical field
The present invention relates to a kind of preparation method of carboxymethyl cellulose lithium, be specifically related to a kind of continuous production method of lithium carboxymethyl cellulose for lithium battery.
Background technology
Along with the development of society, mobile terminal device function is become stronger day by day, and screen enlarging becomes trend; The development of ev industry is also increasingly noticeable.The performance of battery becomes the bottleneck of these industry developments, and preparation has still retention can be stablized, becomes the emphasis of people's research to environment and human body without the battery that dirt is harmful compared with after height ratio capacity, circulation storage especially repeatedly discharge and recharge and big current fast charging and discharging.In all metals, weight is the lightest, redox potential is minimum, specific energy density is the highest for metallic lithium, to environment and human body dirt evil minimum, therefore lithium (ion) battery has the incomparable advantage of traditional plumbic acid, NI-G, nickel-hydrogen accumulator.
Lithium ion battery is a kind of high performance secondary cell, have that operating voltage is high, volume and specific energy density high, have extended cycle life, self-discharge efficiency is low, memory-less effect and do not harm the advantage such as environment and human body, be widely used in mobile communication equipment, notebook computer, take the photograph videocorder, PDA (personal digital assistant), digital camera, power tool and the field such as torpedo, guided missile.In the last few years, lithium ion battery manufacturing technology had had very much progress, and such as certain model is the cylindrical battery capacity of 18650, has brought up to 2400mAh from initial 1200mAh.But with regard to the manufacture method of battery plate (positive plate and negative plate), still continue to use coating process, coating process is divided into oil phase to be coated with and aqueous phase is coated with two kinds.The tamanori that oil phase coating is commonly used has polyvinylidene difluoride (PVDF) (PVDF), tetrafluoroethylene (PTFE).Need to use harmful organic solvent owing to dissolving PVDF, and under high temperature, PVDF is easy and lithium metal, lithium carbide (LiC also
6) there is thermopositive reaction, cause battery from heat release and reduce the use properties of battery, the use of PTFE then can increase the resistance of electrode, and these problems make oil soluble binding agent use to be restricted.Water-soluble binder mainly contains Xylo-Mucine (CMC-Na), SBR emulsion, polyvinyl alcohol, polyacrylic acid, sodium alginate etc.
Carboxymethyl cellulose lithium (CMC-Li) is as a kind of subsidiary material of novel anode material of lithium battery, it is as tamanori that its effect played mainly contains two: one, by positive electrode material, as lithium nickel cobalt-based ternary material, lithium Mn-based material, LiFePO 4 material etc. and running contact close adhesion, keep battery stablizing in charge and discharge process; Two is as a kind of auxiliary positive electrode material, provides a lithium ion storehouse, can improve charging and discharging capacity and the high rate performance of lithium cell.Thus in fact CMC-Li serves the effect to a certain degree improving lithium ion battery usefulness, and its application in field of lithium ion battery is more prevalent.
Carboxymethyl cellulose commercially available is at present all sodium carboxymethyl-cellulose (CMC-Na), belong to ionic cellulose ethers, it also uses as binding agent in lithium ion battery, but it can not provide lithium ion storehouse, can not improve the usefulness of lithium ion battery.And the preparation of CMC-Na normally obtains through alkalization, etherificate, neutralization and washing.Adopt traditional CMC-Na preparation technology to prepare CMC-Li and there is shortcomings: the alkalescence of LiOH is much smaller than NaOH, and solubleness, also much smaller than NaOH, makes in alkalinization, and Mierocrystalline cellulose contacts with alkali lye uneven, alkalization not exclusively, cannot obtain highly purified product; And free alkali is too much, in etherification procedure, etherifying agent utilization ratio is low, and by product increases; And LiOH price is higher, be also not suitable for a large amount of for alkalinized celluloses.Therefore, with preparation CMC-Na processing method prepared by CMC-Li product substitution value low, not soluble, cohesive force is weak, and cost is higher, and these seriously limit the use of CMC-Li as lithium ion battery subsidiary material.
Summary of the invention
The object of the invention is the contaminate environment in order to solve lithium ion battery binding agent, function singleness, the problem such as expensive, and provide a kind of can industrialization, lower-cost lithium carboxymethyl cellulose for lithium battery continuous production technology.
The present invention is achieved by the following technical solution:
A kind of continuous production method of lithium carboxymethyl cellulose for lithium battery comprises step:
(1) preparation of Xylo-Mucine:
A. alkalize: cotton fibre is torn up aqueous sodium hydroxide solution that is rear and 30-55%, the aqueous ethanolic solution being greater than 70-98% together with concentration drops in kneader, feed intake after terminating, get rid of the air in kneader, rare gas element is filled with in kneader, alkalize 40-120 minute under protection of inert gas, and alkalization temperature is 10-40 DEG C;
B. etherificate: etherifying agent is the chloroacetic ethanolic soln of 50-80%, sprayed etherifying agent in kneader equably, is warming up to 75-80 DEG C gradually in 60 minutes, continued reaction 30-120 minute;
C. purify: remove ethanol residual in material through stripping operation;
(2) Xylo-Mucine is acidified, obtains carboxymethyl cellulose hydrogen;
(3) carboxymethyl cellulose hydrogen is immersed in organic solvent system, obtains carboxymethyl cellulose lithium through lithiumation.
Described sodium hydroxide or the non-specified otherwise of other solution are massfraction.
Further, in described step (1), the polymerization degree of raw materials cotton fibre is 500-3000.
Further, the acid that acidifying uses in described step (2) is sulfuric acid, one or more mixing in hydrochloric acid, acetic acid, and acidificatoin time is 40-120min, and souring temperature is 10-40 DEG C.
Further optimization, in described step (2), acid dissolve forms acidizing fluid and carries out acidifying to Xylo-Mucine again in water or organic solvent, the massfraction of described acidizing fluid is 5-20%, and the mass ratio of acidizing fluid and Xylo-Mucine dry sample is (5-16): 1.
Further, acid-soluble in organic solvent in described step (2), described organic solvent is one or more mixing in ethanol, propyl alcohol, Virahol.
Further, the water capacity of the Xylo-Mucine that described step (1) is obtained is 5-50%, and the carboxymethyl cellulose hydrogen water capacity that described step (2) obtains is 60-90%.
Further, described step (3) concrete steps are:
The carboxymethyl cellulose hydrogen that step (2) is obtained is immersed in organic solvent system, obtain carboxymethyl cellulose lithium through quaternization, described organic solvent system is a kind of aqueous solution in ethanol, propyl alcohol, Virahol, acetone or the aqueous solution of several mixing.
Further, the lithium hydroxide aqueous solution that the lithiumation solution used in described step (3) is 3-10% for massfraction, the consumption of described lithium hydroxide and the mass ratio of CMC-H dry sample are (0.15-0.35): 1, and the lithiumation time is 0.5-4h, and temperature is 20-60 DEG C.
Further, in the organic solvent system of described carboxymethyl cellulose hydrogen submergence, the mass ratio of organic solvent and water is (1-1.4): 1.
The substitution value of carboxymethyl cellulose lithium obtained is according to the method described above at 0.6-1.3, and 1% dry sample viscosity is at 100-4000cP, and 2% dry sample transmittance is more than 95.0%, and acid is sticky than 1-1.5, and salt is sticky compares 0.7-1.1.
The CMC-Li that the present invention prepares and poly(vinylidene fluoride) (PVDF), CMC-Na adds in iron phosphate lithium-based lithium cell with equal proportion respectively, is 0.2mA/cm in current density
2, the first charge-discharge specific storage of CMC-Li improves 22%/14.7% and 27.5%/12.3% (CMC-Li183.8/179.5mAhg than PVDF and CMC-Na respectively
-1, PVDF150.4/140.8mAhg
-1, CMC-Na160.2/159.8mAhg
-1), wherein the substitution value of CMC-Na with CMC-Li is identical.
CMC-Li and the PVDF prepared, CMC-Na add in iron phosphate lithium-based lithium cell with equal proportion respectively, after carrying out 200 circle cycle charge-discharges with 0.1C multiplying power, CMC-Li base lithium cell specific discharge capacity is that 175mAh/g is all higher than CMC-Na and PVDF base lithium cell, compare with initial discharge specific storage and only lose 3.31%, and the loss of PVDF base lithium cell is close to 19.4%.Wherein the substitution value of CMC-Li with CMC-Na is identical.
CMC-Li and the PVDF prepared, CMC-Na add in iron phosphate lithium-based lithium cell with equal proportion respectively, with different multiplying 0.1C, 0.2C, 0.5C, 1C, 2C, 5C cycle charge-discharge, CMC-Li base lithium cell is all high than the charging and discharging capacity of CMC-Na and the PVDF base lithium cell under equal multiplying power under different multiplying.
The application of CMC-Li in battery binding agent puts forward recently, correlative study is still underway, and the domestic producer almost not producing CMC-Li in batches at present, we's rule has done a few thing in CMC-Li suitability for industrialized production, in conjunction with domestic production present situation, on the basis ensureing CMC-Li performance, the serialization of CMC-Li, production in enormous quantities can be met, and production cost reduces greatly.In addition, the present invention also added a series of product performance test index, wherein lithiumation rate testing performance index can illustrate that the CMC of the method to extensive substitution value has general applicability, especially to the CMC of comparatively high substitution value (CMC substitution value is more than 1.2), the lithiumation rate (more than 93%) that product reaches higher can still be ensured; This parameters in series is the quality control index of volume production CMC-Li, and also can set up for the standard after CMC-Li industrialization in future provides reference.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described.Described embodiment is only the preferred embodiments of the present invention, is not limited to the present invention, and for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.Wherein, the substitution value test of CMC-Na records according to GB1904-2005, and the strength of solution in embodiment is unspecified is massfraction.
Embodiment 1
(1) preparation of CMC-H: the CMC-Na performance index of preparation are: DS=0.93, water capacity 34.5%, 1% dry sample viscosity 4119cP, purity 99.0%.80gCMC-Na being scattered in massfraction is in the sulfuric acid acidation liquid of 20%, and the mass ratio of acidizing fluid and CMC-Na dry sample is 10:1, acidification reaction 2h at 20 DEG C, filters de-liquid, obtains CMC-H.Then washing several to pH with flowing water is 3-6.Need not dry, pulverization process.
(2) preparation of CMC-Li: join in ethanol/water solvent system by the CMC-H wet feed 180g obtained, CMC-H wet feed water capacity is 75.0%.The mass ratio of ethanol/water solvent and CMC-H dry sample is: 19.7:1.Then add the LiOH aqueous solution that 152.0g massfraction is 10.0%, the mass ratio of lithium hydroxide and CMC-H dry sample is 0.34:1.In system, the mass ratio of second alcohol and water is: 1.18:1.Above-mentioned mixed solution is reacted 2h at 40 DEG C, is then neutralized to pH=7-9 with Glacial acetic acid, filtering de-liquid, is the washing with alcohol of 80% by concentration, and the de-liquid of filtration, oven dry, pulverizing obtain CMC-Li.
The CMC-Li performance index of gained: DS=0.88,1% Aqueous Solution Viscosity 606cP, 2% aqueous solution transmittance 95.2%, purity 99.5%, acid is sticky than 1.08, and salt is sticky than 0.76, lithiumation rate 94.6%, Na salt≤0.10%wt.
Embodiment 2
(1) preparation of CMC-H: the CMC-Na performance index of preparation are: DS=0.93, water capacity 34.5%, 1% dry sample viscosity 4119cP, purity 99.0%.80gCMC-Na being scattered in massfraction is in the sulfuric acid acidation liquid of 15%, and the mass ratio of acidizing fluid and CMC-Na dry sample is 10:1, acidification reaction 50min at 30 DEG C, filters de-liquid, obtains CMC-H.Then washing several to pH with flowing water is 3-6.Need not dry, pulverization process.
(2) preparation of CMC-Li: join in ethanol/water solvent system by the CMC-H wet feed 180g obtained, CMC-H wet feed water capacity is 75.0%.The mass ratio of ethanol/water solvent and CMC-H dry sample is: 17.7:1.Then add the LiOH aqueous solution that 243.7g massfraction is 5.2%, the mass ratio of lithium hydroxide and CMC-H dry sample is 0.25:1.In system, the mass ratio of second alcohol and water is: 1.13:1.Above-mentioned mixed solution is reacted 2h at 45 DEG C, is then neutralized to pH=7-9 with Glacial acetic acid, filtering de-liquid, is the washing with alcohol of 80% by concentration, and the de-liquid of filtration, oven dry, pulverizing obtain CMC-Li.
The CMC-Li performance index of gained: DS=0.88,1% Aqueous Solution Viscosity 2463cP, 2% aqueous solution transmittance 96.0%, purity 99.5%, acid is sticky than 1.41, and salt is sticky than 1.00, lithiumation rate 94.6%, Na salt≤0.10%wt.
Embodiment 3
(1) preparation of CMC-H: the CMC-Na performance index of preparation are: DS=0.91, water capacity 9.3%, 1% dry sample viscosity 3243cP, purity 99.0%.55gCMC-Na being scattered in concentration is in the sulfuric acid acidation liquid of 15%, and the mass ratio of acidizing fluid and CMC-Na dry sample is 10:1, acidification reaction 50min at 30 DEG C, filters de-liquid, obtains CMC-H.Then washing several to pH with flowing water is 3-6.Not oven dry, pulverization process.
(2) preparation of CMC-Li: join in ethanol/water solvent system by the CMC-H wet feed 210g obtained, CMC-H wet feed water capacity is 78.7%.The mass ratio of ethanol/water solvent and CMC-H dry sample is: 20.0:1.Then add the LiOH aqueous solution that 174.0g massfraction is 7.2%, the mass ratio of lithium hydroxide and CMC-H dry sample is 0.28:1.In system, the mass ratio of second alcohol and water is: 1.28:1.Above-mentioned mixed solution is reacted 2h at 45 DEG C, is then neutralized to pH=7-9 with Glacial acetic acid, filtering de-liquid, is the washing with alcohol of 80% by concentration, and the de-liquid of filtration, oven dry, pulverizing obtain CMC-Li.
The CMC-Li performance index of gained: DS=0.85,1% Aqueous Solution Viscosity 1660cP, 2% aqueous solution transmittance 96.6%, purity 99.5%, acid is sticky than 1.31, and salt is sticky than 0.82, lithiumation rate 93.4%, Na salt≤0.10%wt.
Embodiment 4
(1) preparation of CMC-H: the CMC-Na performance index of preparation are: DS=1.45, water capacity 9.3%, it is 120cP that Brookfield viscometer records 2% Aqueous Solution Viscosity, purity 98.3%.50gCMC-Na being scattered in concentration is in the Hydrochloric Acidizing Fluid of 10%, and the mass ratio of acidizing fluid and CMC-Na dry sample is 15:1, acidification reaction 2h at 30 DEG C, filters de-liquid, obtains CMC-H.Then washing several to pH with flowing water is 3-6.Not oven dry, pulverization process.
(2) preparation of CMC-Li: join in ethanol/water solvent system by the CMC-H wet feed 110g obtained, CMC-H wet feed water capacity is 67.2%.The mass ratio of ethanol/water solvent and CMC-H dry sample is: 12.0:1.Then add the LiOH aqueous solution that 149.3g massfraction is 6.88%, the mass ratio of lithium hydroxide and CMC-H dry sample is 0.28:1.In system, the mass ratio of second alcohol and water is: 1.32:1.Above-mentioned mixed solution is reacted 2h at 50 DEG C, is then neutralized to pH=7-9 with Glacial acetic acid, filtering de-liquid, is the washing with alcohol of 80% by concentration, and the de-liquid of filtration, oven dry, pulverizing obtain CMC-Li.
The CMC-Li performance index of gained: DS=1.43,2% Aqueous Solution Viscosity 112cP, 2% aqueous solution transmittance 96.0%, purity 99.8%, acid is sticky than 1.12, and salt is sticky than 0.94, lithiumation rate 98.6%, Na salt≤0.12%wt.
Embodiment 5
(1) preparation of CMC-H: the CMC-Na performance index of preparation are: DS=0.73, Brookfield viscometer records 2% dry sample Aqueous Solution Viscosity 8500cP, purity 98.5%.Be scattered in by 50gCMC-Na in 90% ethanol system, bath raio is 10.0:1, and the HCl aqueous solution 150g concentration adding massfraction 20% is the hydrochloric acid of 20%, acidification reaction 2h at 35 DEG C, filters de-liquid, obtains CMC-H.Then washing several to pH with flowing water is 3-6.Not oven dry, pulverization process.
(2) preparation of CMC-Li: join in ethanol/water solvent system by the CMC-H wet feed 120g obtained, CMC-H wet feed water capacity is 64.9%.The mass ratio of ethanol/water solvent and CMC-H dry sample is: 15.0:1.Then add the LiOH aqueous solution that 102.6g massfraction is 7.0%, the mass ratio of lithium hydroxide and CMC-H dry sample is 0.17:1.In system, the mass ratio of second alcohol and water is: 1.09:1.Above-mentioned mixed solution is reacted 2h at 45 DEG C, is then neutralized to pH=7-9 with Glacial acetic acid, filtering de-liquid, is the washing with alcohol of 80% by concentration, and the de-liquid of filtration, oven dry, pulverizing obtain CMC-Li.
The CMC-Li performance index of gained: DS=0.69,2% Aqueous Solution Viscosity 8000cP, 2% aqueous solution transmittance 98.1%, purity 99.5%, acid is sticky than 1.37, and salt is sticky than 0.69, lithiumation rate 94.5%, Na salt≤0.13wt%.
CMC-Na in embodiment 1-5 is prepared according to following methods:
A. alkalize: cotton fibre is torn up aqueous sodium hydroxide solution that is rear and 30-55%, the aqueous ethanolic solution being greater than 70-98% together with concentration drops in kneader, feed intake after terminating, get rid of the air in kneader, rare gas element is filled with in kneader, alkalize 40-120 minute under protection of inert gas, and alkalization temperature is 10-40 DEG C;
B. etherificate: etherifying agent is the chloroacetic ethanolic soln of 50-80%, sprayed etherifying agent in kneader equably, is warming up to 75-80 DEG C gradually in 60 minutes, continued reaction 30-120 minute;
C. purify: remove ethanol residual in material through stripping operation.
Claims (10)
1. a continuous production method for lithium carboxymethyl cellulose for lithium battery, is characterized in that: comprise step:
(1) preparation of Xylo-Mucine:
A. alkalize: cotton fibre is torn up aqueous sodium hydroxide solution that is rear and 30-55%, the aqueous ethanolic solution being greater than 70-98% together with concentration drops in kneader, feed intake after terminating, get rid of the air in kneader, rare gas element is filled with in kneader, alkalize 40-120 minute under protection of inert gas, and alkalization temperature is 10-40 DEG C;
B. etherificate: etherifying agent is the chloroacetic ethanolic soln of 50-80%, sprayed etherifying agent in kneader equably, is warming up to 75-80 DEG C gradually in 60 minutes, continued reaction 30-120 minute;
C. purify: remove ethanol residual in material through stripping operation;
(2) Xylo-Mucine is acidified, obtains carboxymethyl cellulose hydrogen;
(3) carboxymethyl cellulose hydrogen is immersed in organic solvent system, obtains carboxymethyl cellulose lithium through lithiumation.
2. the continuous production method of lithium carboxymethyl cellulose for lithium battery according to claim 1, is characterized in that: in described step (1), the polymerization degree of raw materials cotton fibre is 500-3000.
3. the continuous production method of lithium carboxymethyl cellulose for lithium battery according to claim 1 and 2, it is characterized in that: the acid that acidifying uses in described step (2) is sulfuric acid, one or more mixing in hydrochloric acid, acetic acid, acidificatoin time is 40-120min, and souring temperature is 10-40 DEG C.
4. the continuous production method of lithium carboxymethyl cellulose for lithium battery according to claim 1 and 2, it is characterized in that: in described step (2), acid dissolve forms acidizing fluid and carries out acidifying to Xylo-Mucine again in water or organic solvent, the massfraction of described acidizing fluid is 5-20%, and the mass ratio of acidizing fluid and Xylo-Mucine dry sample is (5-16): 1.
5. the continuous production method of lithium carboxymethyl cellulose for lithium battery according to claim 4, it is characterized in that: acid-soluble in organic solvent in described step (2), described organic solvent is one or more mixing in ethanol, propyl alcohol, Virahol.
6. the continuous production method of lithium carboxymethyl cellulose for lithium battery according to claim 1 and 2, it is characterized in that: the water capacity of the Xylo-Mucine that described step (1) is obtained is 5-50%, and the carboxymethyl cellulose hydrogen water capacity that described step (2) obtains is 60-90%.
7. the continuous production method of lithium carboxymethyl cellulose for lithium battery according to claim 1 and 2, is characterized in that: described step (3) concrete steps are:
The carboxymethyl cellulose hydrogen that step (2) is obtained is immersed in organic solvent system, obtain carboxymethyl cellulose lithium through quaternization, described organic solvent system is a kind of aqueous solution in ethanol, propyl alcohol, Virahol, acetone or the aqueous solution of several mixing.
8. the continuous production method of lithium carboxymethyl cellulose for lithium battery according to claim 7, it is characterized in that: the lithium hydroxide aqueous solution that the lithiumation solution used in described step (3) is 3-10% for massfraction, the consumption of described lithium hydroxide and the mass ratio of CMC-H dry sample are (0.15-0.35): 1, the lithiumation time is 0.5-4h, and temperature is 20-60 DEG C.
9. the continuous production method of lithium carboxymethyl cellulose for lithium battery according to claim 7, is characterized in that: in the organic solvent system of described carboxymethyl cellulose hydrogen submergence, the mass ratio of organic solvent and water is (1-1.4): 1.
10. the carboxymethyl cellulose lithium that the continuous production method of lithium carboxymethyl cellulose for lithium battery as claimed in any of claims 1 to 9 is obtained, it is characterized in that: the substitution value of described carboxymethyl cellulose lithium is 0.6-1.3,1% dry sample viscosity is 100-4000cP, 2% dry sample transmittance is more than 95.0%, acid is sticky compares 0.6-1.5, salt is sticky than 0.6-1.5, lithiumation rate more than 94%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510742242.2A CN105330751A (en) | 2015-11-05 | 2015-11-05 | Continuous production method of carboxymethylcellulose lithium for lithium batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510742242.2A CN105330751A (en) | 2015-11-05 | 2015-11-05 | Continuous production method of carboxymethylcellulose lithium for lithium batteries |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105330751A true CN105330751A (en) | 2016-02-17 |
Family
ID=55281534
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510742242.2A Pending CN105330751A (en) | 2015-11-05 | 2015-11-05 | Continuous production method of carboxymethylcellulose lithium for lithium batteries |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105330751A (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105720224A (en) * | 2016-03-28 | 2016-06-29 | 北京理工大学 | Novel nano-crystalline cellulose modified lithium ion battery diaphragm and preparation method thereof |
| CN105949329A (en) * | 2016-05-24 | 2016-09-21 | 江苏泰利达新材料股份有限公司 | Production process of ultrahigh viscosity sodium carboxymethyl cellulose |
| CN106336461A (en) * | 2016-08-22 | 2017-01-18 | 四川北方硝化棉股份有限公司 | Preparation method of carboxymethyl cellulose lithium |
| 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 |
| CN109360976A (en) * | 2018-12-03 | 2019-02-19 | 重庆力宏精细化工有限公司 | A kind of negative electrode material of lithium battery and its preparation method and application |
| CN109535264A (en) * | 2018-11-29 | 2019-03-29 | 瑞红锂电池材料(苏州)有限公司 | A kind of preparation method and application of CMCLi |
| CN111363049A (en) * | 2019-11-21 | 2020-07-03 | 重庆纤磊新材料科技有限公司 | Method for synthesizing ultrahigh-viscosity lithium carboxymethyl cellulose with ultralow solvent system |
| 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 |
| CN113265008A (en) * | 2021-07-02 | 2021-08-17 | 重庆力宏精细化工有限公司 | High-viscosity lithium carboxymethyl cellulose and preparation method and application thereof |
| CN113471512A (en) * | 2021-05-12 | 2021-10-01 | 广州明美新能源股份有限公司 | Low-temperature lithium battery |
| CN113773510A (en) * | 2021-09-07 | 2021-12-10 | 重庆理工大学 | Production method of lithium carboxymethyl cellulose grafted lithium polyacrylate |
| CN114920853A (en) * | 2022-06-29 | 2022-08-19 | 重庆力宏精细化工有限公司 | Flexible carboxymethyl cellulose ether and preparation method and application thereof |
| CN115215945A (en) * | 2022-08-08 | 2022-10-21 | 大连中比动力电池有限公司 | Lithium carboxymethyl cellulose and preparation method thereof |
| CN115636882A (en) * | 2022-11-14 | 2023-01-24 | 常德市大度新材料有限公司 | Preparation method of lithium carboxymethyl cellulose |
| CN116217742A (en) * | 2022-09-23 | 2023-06-06 | 常熟威怡科技有限公司 | Carboxymethyl cellulose lithium |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101220099A (en) * | 2008-01-31 | 2008-07-16 | 重庆力宏精细化工有限公司 | Production method for high viscosity sodium carboxymethylcellulose |
| CN102206286A (en) * | 2011-05-16 | 2011-10-05 | 北京理工大学 | Preparation method of lithium carboxymethyl cellulose for lithium battery |
| CN103059144A (en) * | 2013-02-04 | 2013-04-24 | 重庆力宏精细化工有限公司 | Preparation method of high-viscosity pelletizing sodium carboxymethylcellulose |
| US20140242452A1 (en) * | 2013-02-27 | 2014-08-28 | GM Global Technology Operations LLC | Lithium ion battery |
-
2015
- 2015-11-05 CN CN201510742242.2A patent/CN105330751A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101220099A (en) * | 2008-01-31 | 2008-07-16 | 重庆力宏精细化工有限公司 | Production method for high viscosity sodium carboxymethylcellulose |
| CN102206286A (en) * | 2011-05-16 | 2011-10-05 | 北京理工大学 | Preparation method of lithium carboxymethyl cellulose for lithium battery |
| CN103059144A (en) * | 2013-02-04 | 2013-04-24 | 重庆力宏精细化工有限公司 | Preparation method of high-viscosity pelletizing sodium carboxymethylcellulose |
| US20140242452A1 (en) * | 2013-02-27 | 2014-08-28 | GM Global Technology Operations LLC | Lithium ion battery |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105720224A (en) * | 2016-03-28 | 2016-06-29 | 北京理工大学 | Novel nano-crystalline cellulose modified lithium ion battery diaphragm and preparation method thereof |
| CN105949329A (en) * | 2016-05-24 | 2016-09-21 | 江苏泰利达新材料股份有限公司 | Production process of ultrahigh viscosity sodium carboxymethyl cellulose |
| CN106336461B (en) * | 2016-08-22 | 2018-09-11 | 四川北方硝化棉股份有限公司 | A kind of preparation method of carboxymethyl cellulose lithium |
| CN106336461A (en) * | 2016-08-22 | 2017-01-18 | 四川北方硝化棉股份有限公司 | Preparation method of carboxymethyl cellulose lithium |
| 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 |
| CN106366203B (en) * | 2016-08-31 | 2019-05-07 | 泸州北方化学工业有限公司 | A kind of preparation method of Cardia Salt carboxymethyl cellulose lithium |
| CN109535264A (en) * | 2018-11-29 | 2019-03-29 | 瑞红锂电池材料(苏州)有限公司 | A kind of preparation method and application of CMCLi |
| CN109360976A (en) * | 2018-12-03 | 2019-02-19 | 重庆力宏精细化工有限公司 | A kind of negative electrode material of lithium battery and its preparation method and application |
| CN111363049A (en) * | 2019-11-21 | 2020-07-03 | 重庆纤磊新材料科技有限公司 | Method for synthesizing ultrahigh-viscosity lithium carboxymethyl cellulose with ultralow solvent system |
| 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 |
| CN113471512A (en) * | 2021-05-12 | 2021-10-01 | 广州明美新能源股份有限公司 | Low-temperature lithium battery |
| CN113265008A (en) * | 2021-07-02 | 2021-08-17 | 重庆力宏精细化工有限公司 | High-viscosity lithium carboxymethyl cellulose and preparation method and application thereof |
| US20230002511A1 (en) * | 2021-07-02 | 2023-01-05 | Chongqing Lihong Fine Chemicals Co., Ltd | High-viscosity lithium carboxymethyl cellulose and preparation method therefor and application thereof |
| JP7377897B2 (en) | 2021-07-02 | 2023-11-10 | 重慶力宏精細化工有限公司 | Preparation method and use of high viscosity carboxymethyl cellulose lithium |
| US11608387B2 (en) * | 2021-07-02 | 2023-03-21 | Chongqing Lihong Fine Chemicals Co., Ltd | High-viscosity lithium carboxymethyl cellulose and preparation method therefor and application thereof |
| WO2023273367A1 (en) * | 2021-07-02 | 2023-01-05 | 重庆力宏精细化工有限公司 | High-viscosity lithium carboxymethyl cellulose, preparation method therefor, and application thereof |
| DE102022104702A1 (en) | 2021-07-02 | 2023-01-05 | Chongqing Lihong Fine Chemicals Co., Ltd | HIGH VISCOSITY LITHIUMCARBOXYMETHYLCELLULOSE AND METHOD OF PRODUCTION THEREOF AND USE THEREOF |
| CN113773510A (en) * | 2021-09-07 | 2021-12-10 | 重庆理工大学 | Production method of lithium carboxymethyl cellulose grafted lithium polyacrylate |
| CN114920853A (en) * | 2022-06-29 | 2022-08-19 | 重庆力宏精细化工有限公司 | Flexible carboxymethyl cellulose ether and preparation method and application thereof |
| CN115215945A (en) * | 2022-08-08 | 2022-10-21 | 大连中比动力电池有限公司 | Lithium carboxymethyl cellulose and preparation method thereof |
| CN116217742A (en) * | 2022-09-23 | 2023-06-06 | 常熟威怡科技有限公司 | Carboxymethyl cellulose lithium |
| CN116217742B (en) * | 2022-09-23 | 2024-03-26 | 常熟威怡科技有限公司 | Carboxymethyl cellulose lithium |
| CN115636882A (en) * | 2022-11-14 | 2023-01-24 | 常德市大度新材料有限公司 | Preparation method of lithium carboxymethyl cellulose |
| CN115636882B (en) * | 2022-11-14 | 2023-08-11 | 常德市大度新材料有限公司 | Preparation method of lithium carboxymethyl cellulose |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105330751A (en) | Continuous production method of carboxymethylcellulose lithium for lithium batteries | |
| KR102235389B1 (en) | Acrylonitrile copolymer adhesive and its application in lithium ion batteries | |
| CN108987800B (en) | Solid electrolyte, preparation method thereof and solid battery containing solid electrolyte | |
| WO2018000579A1 (en) | Multifunctionalized modified polymer binder for lithium ion battery and use thereof in electrochemical energy storage device | |
| WO2016188477A2 (en) | Carbon-coated ternary positive electrode material, preparation method therefor, and lithium ion battery | |
| CN103117414B (en) | A kind of negative pole lithium titanate battery electrolyte, lithium ion battery and preparation method thereof | |
| CN101764253B (en) | Secondary aluminum battery and preparation method thereof | |
| CN109004220B (en) | Boric acid compound modified lithium ion battery silicon cathode and preparation method thereof | |
| CN109155414B (en) | Binder composition for solid electrolyte battery, and slurry composition for solid electrolyte battery | |
| CN108470884B (en) | Lithium ion battery electrode prepared from water-based binder | |
| CN107359351B (en) | Humic acid-based water-based binder for lithium ion battery and method for preparing electrode plate by using same | |
| CN110061239B (en) | Lignin-based binder, preparation method thereof and lithium ion battery | |
| CN111129457A (en) | Aqueous ternary cathode slurry and preparation method thereof | |
| WO2017121113A1 (en) | Carbon-coated zinc ferrite electrode material, and preparation method and application thereof | |
| JP2018198199A (en) | Aqueous binder resin composition, slurry for nonaqueous battery, nonaqueous battery electrode, nonaqueous battery separator, and nonaqueous battery | |
| CN111326738A (en) | Binder for silicon-based negative electrode material and preparation method thereof | |
| CN103187556A (en) | Lithium ion battery and anode material thereof, preparation method | |
| CN106336461A (en) | Preparation method of carboxymethyl cellulose lithium | |
| CN113659145A (en) | Cathode slurry and preparation method thereof, and lithium ion battery and preparation method thereof | |
| CN115566170A (en) | Preparation method of high-energy-density quick-charging lithium ion battery cathode material | |
| CN109802127B (en) | Preparation method of silver-doped ferroferric oxide nano composite material | |
| CN108336319B (en) | Silicon-carbon negative electrode material and preparation method and application thereof | |
| JP6922456B2 (en) | Lithium-ion battery positive electrode binder aqueous solution, lithium-ion battery positive electrode powder binder, lithium-ion battery positive electrode slurry, lithium-ion battery positive electrode, lithium-ion battery | |
| CN109659562A (en) | Binder, electrode slice and lithium ion battery for lithium ion battery | |
| CN110492101B (en) | Lithium ion battery cathode binder and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 400000, Longshan Road, Longshan, Chongqing, No. 7, No. 19-6, Longhu, 3-2 purple capital city, Yubei District Applicant after: Chongqing Lihong Fine Chemicals Co., Ltd. Applicant after: Beijing Institute of Technology Address before: 400000, 7 South Road, 6 Jiang gorge Road, Chongqing Applicant before: Chongqing Lihong Fine Chemicals Co., Ltd. Applicant before: Beijing Institute of Technology |
|
| COR | Change of bibliographic data | ||
| CB02 | Change of applicant information |
Address after: 400000 Chongqing City, South Bank of the Yangtze River Road, No. 6 Applicant after: Chongqing Lihong Fine Chemicals Co., Ltd. Applicant after: Beijing Institute of Technology Address before: 400000, Longshan Road, Longshan, Chongqing, No. 7, No. 19-6, Longhu, 3-2 purple capital city, Yubei District Applicant before: Chongqing Lihong Fine Chemicals Co., Ltd. Applicant before: Beijing Institute of Technology |
|
| COR | Change of bibliographic data | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160217 |