CN106336461B - A kind of preparation method of carboxymethyl cellulose lithium - Google Patents
A kind of preparation method of carboxymethyl cellulose lithium Download PDFInfo
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- 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 present invention discloses a kind of preparation method of carboxymethyl cellulose lithium, includes the following steps：(1) alkalization (2) etherificate (3) is neutralized, washing, drying, is crushed.The present invention first uses lithium hydroxide activation, alkalinized celluloses, then carries out etherification reaction, finally obtains carboxymethyl cellulose lithium.Simplification of flowsheet of the present invention reduces reaction time, reduces material loss, prepares high viscosity carboxymethyl cellulose.
Description
Technical field
The present invention relates to a kind of preparation methods of carboxymethyl cellulose lithium, belong to natural macromolecular material chemical modification neck
Domain.
Background technology
With the worsening shortages of the chemical fuel resource in global range, people is forced to find novel alternative cleaning energy
Source.Battery due to the use of convenient, cheap, light weight, cycle storage life length, stable operating voltage, to environmental beneficial and
As ideal alternative energy source.In chemical cell, due to lithium metal is most light in all metals, oxidation-reduction potential is minimum,
Mass energy density is maximum, therefore lithium (ion) battery has traditional plumbic acid, ni-Cd, nickel-metal hydride battery unrivaled excellent
Point.
Lithium ion battery is a kind of high performance secondary cell, volume and weight energy density height high with operating voltage,
Long lifespan, self discharge efficiency is low, memory-less effect and it is environmentally friendly the advantages that, be widely used in mobile communication equipment, notes
This computer takes the photograph the fields such as videocorder, PDA (personal digital assistant), digital camera, electric tool and torpedo, guided missile.In recent years
Come, lithium ion battery manufacturing technology has great progress so that such as capacity of the cylindrical battery of model 18650, from initial
1200mAh be increased to 2400mAh.But for the manufacturing method of battery pole piece (positive plate and negative plate), still continue to use coating
Method.Coating method is divided to oil phase coating and water phase to be coated with two kinds.Currently, in large-scale production pole piece, oil phase is generally still used
Coating technique.Currently, being fluoropolymer adhesive using most adhesives.Such as：Using Kynoar (PVDF), N-
Methylpyrrolidone solution is binder, using Fluorine containing olefine polymer as the adhesive of lithium ion battery electrode material, is being made
Environment is not only polluted in the volatilization of solvent in the process, but also endangers the health of operating personnel.In addition fluoropolymer-containing solvent is expensive,
Undoubtedly increase the production cost of lithium ion battery.
Presently commercially available carboxymethyl cellulose is all sanlose (CMC-Na), belongs to ionic cellulose element
Ether, typically through obtained from alkalization, etherificate, neutralization washing.Carboxymethyl cellulose lithium (CMC-Li) is as a kind of novel lithium
The auxiliary material of cell positive material, play the role of it is main there are two：First, as binder, by positive electrode, such as lithium
Nickel cobalt base ternary material, lithium Mn-based material, LiFePO 4 material etc. and current-collector close adhesion keep battery in charge and discharge process
In stabilization；Second is that as a kind of positive electrode of auxiliary, a lithium ion library is provided, the charge and discharge ratio of lithium battery can be improved
Capacity and high rate performance.Thus CMC-Li actually plays the role of improving lithium ion battery efficiency to a certain degree, in lithium
Application in ion battery field is more prevalent.
In CN102206286A patents, a kind of preparation process of carboxymethyl cellulose lithium is described, it is characterised in that system
Standby process is divided into two parts：(1) preparation process 1 of carboxymethyl cellulose acid：By sodium carboxymethylcellulose made from slurry process point
It dissipates in organic solvent, aqueous hydrochloric acid solution is added, obtains mixed solution；Step 2：By the mixed liquor of step 1 at 20 DEG C~50 DEG C
Then lower reaction takes off liquid, obtain crude product carboxymethyl cellulose acid；Step 3：The organic solvent for being 80%~95% with volumetric concentration
The crude product carboxymethyl cellulose acid that washing step 2 obtains, the carboxymethyl cellulose acid application high levels of organic solvents of high substituted degree
It washs, then takes off liquid, drying, crushing, obtain carboxymethyl cellulose acid；(2) preparation process 1 of carboxymethyl cellulose lithium：It will
(1) in organic solvent, LiOH*H is added in the carboxymethyl cellulose acid dispersion obtained in20 aqueous solution, obtains mixed solution；Step
Rapid 2：PH=6~8 are neutralized to glacial acetic acid after the mixed liquor of (two) step 1 is reacted at 40 DEG C~60 DEG C, obtain crude product carboxylic
Methylcellulose lithium；Step 3：After the crude product carboxymethyl cellulose lithium that (two) step 2 obtains is carried out de- liquid, with concentration 75%~
85% organic solvent washing, the carboxymethyl cellulose lithium application high levels of organic solvents of high substituted degree wash；De- liquid, drying,
Crush to obtain carboxymethyl cellulose lithium.That there are process cycles is long for the above method, and material process is lost in the problems such as serious.
Invention content
To solve the above problems, the present invention directly uses lithium hydroxide activation, alkalinized celluloses, then etherification reaction is carried out,
Finally obtain carboxymethyl cellulose lithium.Simplification of flowsheet of the present invention reduces reaction time, reduces material loss, prepares height
Viscosity carboxymethyl cellulose.
Technical scheme is as follows：
A kind of preparation method of carboxymethyl cellulose lithium, includes the following steps：
A, the purified cotton (trade mark M650) of crushing and lithium hydroxide aqueous solution, isopropanol water solution are put into reaction kettle,
Quaternization is carried out under nitrogen atmosphere；
B, after alkalization, etherifying agent is added in the material to reaction kettle, after being sufficiently mixed 40min, heating carries out
Etherification reaction；
C, the lithium hydroxide solution for being slowly added to remainder is reacted；
D, last material obtains carboxymethyl cellulose lithium after neutralization, washing, drying, crushing.
Wherein, the quaternization time is 50~250 minutes in step a, and preferably 120~250 minutes, quaternization temperature was
10~40 DEG C, the mass percent concentration of the lithium hydroxide aqueous solution is 5~13%, is that reaction is situated between with isopropanol water solution
Matter, the mass percentage concentration of isopropanol water solution are 70~98%, lithium hydroxide solid amount and purified cotton mass ratio be 2.5~
4.0：1；Isopropanol water solution and the mass ratio of purified cotton 30~40：1；Lithium hydroxide addition is required addition hydrogen in step a
The 3/5-2/3 of lithia gross mass.
Cellulose alkalizes reaction speed quickly, but the complexity of the morphosis due to cellulose itself, lye and fiber
Sufficiently uniformly suction alkali, swollen, infiltration need time enough, the long cellulose of alkalization time to generate degradation instead to element.
Etherifying agent described in step b is chloroacetic aqueous isopropanol, and mass percent concentration is 50~80%, etherificate
The mass ratio 1.0~4.0 of agent and purified cotton：1, etherification reaction temperature is 40~78 DEG C, and the etherification reaction time is 40~120 points
Clock, reaction carry out at a temperature of two sections, and etherification reaction is divided into etherificate initial stage, mid-term and several stages in later stage, therefore etherification temperature
It is divided into two sections of controls, etherificate initial stage is mainly the neutralization reaction of etherifying agent and free alkali and the mistake permeated into alkali cellulose
Journey, is exothermic reaction, and it is easily long that reaction temperature should control the easy low, time, if initial reaction stage reaction temperature is excessively high, can cause surface layer
Local reaction, keep substitution uneven, therefore first set reaction temperature is advisable with 45~55 DEG C；Etherificate mid-term is etherification reaction master
The stage is wanted, for general control at 60~65 DEG C, etherificate later stage etherificate agent concentration is relatively low, can promote reaction temperature to 70 DEG C or more, from
And improve ether effect.
Etherification stage includes the neutralization reaction of monoxone and alkali, the nucleophilic substitution of monoxone lithium and alkali cellulose, chlorine
Acetic acid is needed by reacting in solvent penetration to cellulose, and the reaction time is insufficient, can cause to replace it is uneven, it is long
Reaction time can reduce utilization rate of equipment and installations, and energy consumption etc. is also corresponding to be increased, therefore controls the etherification reaction time, could improve product
Quality, it is cost-effective.
It is carried out in 40 minutes that the etherification reaction will be after quaternization, main in this way there are two purposes, and one is ether
Agent monoxone fully reacts to form lithium salts participation etherification reaction with lithium hydroxide；Second is to allow etherifying agent fully in alkali cellulose
Middle dispersion infiltration causes to react uneven, causes product inherent quality poor to prevent local reaction from forming parcel-like material.
The amount for the lithium hydroxide being added in step c is the required 1/3-2/5 that lithium hydroxide gross mass is added, the hydroxide
Lithium uses lithium hydroxide in industrial grade solid.
In step d, neutralizer is glacial acetic acid, until neutralization makes material be in neutrality；Using 80%wt ethyl alcohol washed to
It is 3 times few；It is 2 hours dry at 80 DEG C；By crushing rear material more than 200 mesh.
Advantageous effect
The present invention first uses lithium hydroxide activation, alkalinized celluloses, then is etherified using excessive etherifying agent, and part is made
Etherifying agent penetrates into cellulose in advance, then is slowly penetrated into cellulose with lithium hydroxide and carried out instead with excessive etherifying agent
It answers, reduces side reaction, improve etherificate effect, make reaction evenly, while reducing cellulose degradation, improve product viscosity.This hair
Bright method production process technology is simple, and reaction time is short, and equipment investment is few, and consumption of raw materials is low, the carboxylic first produced using this method
Base cellulose lithium not only has good dissolubility, while it is with viscosity higher.
Specific implementation mode
With reference to specific embodiment, the present invention will be further described.The embodiment is only the preferred implementation of the present invention
Example, is not intended to restrict the invention, for those skilled in the art, the present invention can have various changes and change
Change.All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in the present invention
Protection domain within.
Wherein, the degree of substitution test of CMC-Li is measured according to GB 1904-2005, and the solution concentration in embodiment is not special
What is pointed out is mass fraction.
Embodiment 1
200ml isopropanols, 15g lithium hydroxides, 115g water are added in three mouthfuls of sesame seed cakes, is mixed, is added after 10min
The purified cotton that 10g is crushed leads to N2, 20 DEG C alkalization 2.5h, weigh 30.5g monoxones and be dissolved in 22g isopropanols, be added dropwise to three mouthfuls of burnings
40min is mixed in bottle, is warming up to 50 DEG C of etherificate 1h, and 10g lithium hydroxides are dissolved in 77g water, are very slowly added by peristaltic pump
Into three mouthfuls of sesame seed cakes, reacts 1h and be cooled to room temperature after reaction temperature rises to 75 DEG C of reaction 40min, acetic acid neutralization is in neutrality, and is adopted
With 80% isopropanol filtration washing three times after, carry out baking material.
Gained CMC-Li：DS=0.53, rotational viscometer measure 1% Aqueous Solution Viscosity 4100cP, the light transmission of 1% aqueous solution
Rate 35.0%, purity 99.0%, Na salt 0.10%wtD.
Embodiment 2
200ml isopropanols, 12g lithium hydroxides, 93g water are added in three mouthfuls of sesame seed cakes, is mixed, 10g is added later in 10min
The purified cotton of crushing leads to N2, 20 DEG C alkalization 3h, weigh 22g monoxones and be dissolved in 18g isopropanols, be added dropwise in three-necked flask mix
40min is closed, 50 DEG C of etherificate 1h are warming up to, 6g lithium hydroxides are dissolved in 47g water, three mouthfuls of burnings are very slowly added to by peristaltic pump
In cake, reacts 1h and be cooled to room temperature after reaction temperature rises to 75 DEG C of reaction 40min, acetic acid neutralization is in neutrality, different using 80%
Propyl alcohol filtration washing three times after, carry out baking material.
Gained CMC-Li：DS=0.41, rotational viscometer measure 1% Aqueous Solution Viscosity 4200cP, the light transmission of 1% aqueous solution
Rate 37.0%, purity 99.0%, Na salt 0.10%wtD.
Embodiment 3
180ml isopropanols, 15g lithium hydroxides, 115g water are added in three mouthfuls of sesame seed cakes, is mixed, is added after 10min
The purified cotton that 10g is crushed leads to N2, 20 DEG C alkalization 2h, weigh 30.5g monoxones and be dissolved in 22g isopropanols, be added dropwise to three-necked flask
Interior mixing 40min, is warming up to 55 DEG C of etherificate 1h, and 10g lithium hydroxides are dissolved in 77g water, are very slowly added to by peristaltic pump
In three mouthfuls of sesame seed cakes, reacts 1h and be cooled to room temperature after reaction temperature rises to 75 DEG C of reaction 40min, acetic acid neutralization is in neutrality, and is used
80% isopropanol filtration washing three times after, carry out baking material.
Gained CMC-Li：DS=0.49, rotational viscometer measure 1% Aqueous Solution Viscosity 4300cP, the light transmission of 1% aqueous solution
Rate 33.0%, purity 99.0%, Na salt 0.10%wtD.
Comparative example 1
200ml isopropanols, 25g lithium hydroxides, 165g water are added in three mouthfuls of sesame seed cakes, is mixed, 10g is added after 10min
The purified cotton of crushing leads to N2, 20 DEG C alkalization 3.5h, weigh 30.5g monoxones and be dissolved in 22g isopropanols, be added dropwise to three-necked flask
Interior mixing 40min is warming up to 50 DEG C of etherificate 1h, cooling after liter temperature to 75 DEG C of reaction 40min, in being neutralized to glacial acetic acid
Property, using 80% isopropanol filtration washing three times after, carry out baking material.
Gained CMC-Li：DS=0.43, rotational viscometer measure 1% Aqueous Solution Viscosity 4000cP, the light transmission of 1% aqueous solution
Rate 30.0%, purity 99.0%, Na salt 0.10%wtD.
Claims (3)
1. a kind of preparation method of carboxymethyl cellulose lithium, which is characterized in that include the following steps：
A, by the purified cotton of crushing and lithium hydroxide aqueous solution, isopropanol water solution input reaction kettle, under nitrogen atmosphere into
Row quaternization；
B, after alkalization, etherifying agent is added in the material to reaction kettle, after being sufficiently mixed 40min, heating is etherified
Reaction；
C, the lithium hydroxide solution for being slowly added to remainder is reacted；
D, last material obtains carboxymethyl cellulose lithium after neutralization, washing, drying, crushing；
The quaternization time is 50~250 minutes in step a, and quaternization temperature is 10~40 DEG C, and the lithium hydroxide is water-soluble
The mass percent concentration of liquid is 5~13%, and the mass percentage concentration of isopropanol water solution is 70~98%, lithium hydroxide solid
Total amount and purified cotton mass ratio are 2.5~4.0:1；Isopropanol water solution and the mass ratio of purified cotton 30~40:1；Step a hydrogen-oxygens
It is the required 3/5-2/3 that lithium hydroxide gross mass is added to change lithium addition；
Etherifying agent described in step b be chloroacetic aqueous isopropanol, mass percent concentration be 50~80%, etherifying agent and
The mass ratio 1.0~4.0 of purified cotton:1, etherification reaction temperature is 40 DEG C -78 DEG C, and the etherification reaction time is 40~120 minutes；
The amount for the lithium hydroxide being added in step c is the required 1/3-2/5 that lithium hydroxide gross mass is added.
2. a kind of preparation method of carboxymethyl cellulose lithium according to claim 1, which is characterized in that alkalize in step a
Reaction time is 120~250 minutes.
3. a kind of preparation method of carboxymethyl cellulose lithium according to claim 1, which is characterized in that in step d, neutralize
Agent is glacial acetic acid；It is washed at least 3 times using 80%wt ethyl alcohol；It is dried 2 hours at 80 DEG C；Exist by crushing rear material
It is more than 200 mesh.
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| CN107394146A (en) * | 2017-07-10 | 2017-11-24 | 上海应用技术大学 | A kind of anode material for lithium-ion batteries LiFePO4/ C and preparation method thereof |
| CN108300056A (en) * | 2017-08-02 | 2018-07-20 | 天津市捷威动力工业有限公司 | A kind of cathode pole piece of lithium ion secondary battery primary coat coating |
| 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 |
| CN112751034B (en) * | 2020-12-31 | 2022-11-25 | 远景动力技术(江苏)有限公司 | Negative electrode slurry for lithium ion battery, negative electrode, and lithium ion battery |
| CN112759657A (en) * | 2020-12-31 | 2021-05-07 | 远景动力技术(江苏)有限公司 | Lithium carboxymethyl cellulose, preparation method and application thereof |
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