CN111403681A - Negative electrode expanding agent for storage battery - Google Patents
Negative electrode expanding agent for storage battery Download PDFInfo
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- CN111403681A CN111403681A CN202010163639.7A CN202010163639A CN111403681A CN 111403681 A CN111403681 A CN 111403681A CN 202010163639 A CN202010163639 A CN 202010163639A CN 111403681 A CN111403681 A CN 111403681A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- 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
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Abstract
The invention relates to the technical field of battery additive preparation, and particularly discloses a negative electrode expanding agent for a storage battery. The swelling agent comprises the following components: conductive materials, barium sulfate and sodium lignosulfonate; the sodium lignosulfonate is modified sodium lignosulfonate, and is prepared by the following method: (1) adding alkali lignin into an acidic aqueous solution, stirring, filtering, and taking precipitated alkali lignin; (2) adding the precipitated alkali lignin and p-chloromethyl styrene into an organic solvent, mixing, and reacting for 3-5 h at 130-150 ℃; obtaining p-chloromethylstyrylation precipitation alkali lignin; (3) adding p-chloromethylstyrenated precipitated alkali lignin into an aqueous solution containing sodium sulfite, adjusting the pH value to 13-14, reacting for 2-3 h at 130-150 ℃, and taking the product to obtain the modified sodium lignosulfonate. The negative electrode expanding agent for the storage battery can effectively improve the performance of the storage battery, particularly the deep cycle life.
Description
Technical Field
The invention relates to the technical field of battery additive preparation, in particular to a negative electrode expanding agent for a storage battery.
Background
In the practical production process, in order to improve the convenience of production, a negative electrode expanding agent consisting of the conductive material, the barium sulfate and the sodium lignosulfonate is usually directly purchased and then directly mixed with the lead powder, the sulfuric acid and the water to obtain the negative electrode lead paste.
Disclosure of Invention
The invention aims to solve the technical problem of providing a negative electrode expanding agent for a storage battery. The negative electrode expanding agent for the storage battery can effectively prolong the deep cycle life of the storage battery.
The technical problem to be solved by the invention is realized by the following technical scheme:
a negative electrode expander for a secondary battery, comprising the following components: conductive materials, barium sulfate and sodium lignosulfonate;
the sodium lignosulfonate is modified sodium lignosulfonate, and is prepared by the following method:
(1) adding alkali lignin into an acidic aqueous solution, stirring, filtering, and taking precipitated alkali lignin;
(2) adding the precipitated alkali lignin and p-chloromethyl styrene into an organic solvent, mixing, and reacting for 3-5 h at 130-150 ℃; obtaining p-chloromethylstyrylation precipitation alkali lignin;
(3) adding p-chloromethylstyrenated precipitated alkali lignin into an aqueous solution containing sodium sulfite, adjusting the pH value to 13-14, reacting for 2-3 h at 130-150 ℃, and taking the product to obtain the modified sodium lignosulfonate.
Preferably, the acidic aqueous solution in the step (1) is an acidic aqueous solution with a pH value of 2-3; the dosage of the acidic aqueous solution is 3-5 times of that of the alkali lignin; most preferably, the acidic aqueous solution in step (1) is an acidic aqueous solution with a pH value of 3; the dosage of the acidic aqueous solution is 4 times of that of the alkali lignin.
Preferably, the alkali lignin in step (1) is wheat straw alkali lignin.
Preferably, the weight using amount ratio of the precipitated alkali lignin to the p-chloromethyl styrene in the step (2) is 2-3: 1.
Most preferably, the weight ratio of precipitated alkali lignin to p-chloromethylstyrene in step (2) is 2.5: 1.
Preferably, the organic solvent in step (2) is ethanol.
Preferably, step (2) is carried out at 140 ℃ for 4 h.
Preferably, the mass fraction of the aqueous solution of sodium sulfite in the step (3) is 20-30%; the weight of the aqueous solution containing sodium sulfite is 3-5 times of the weight of the p-chloromethylstyrylation precipitation alkali lignin.
Preferably, the conductive material is selected from one or a mixture of more than two of carbon black, carbon nanotubes and graphene; the barium sulfate is selected from precipitated barium sulfate.
Preferably, in the negative electrode expanding agent for the storage battery, the conductive material, the barium sulfate and the sodium lignosulfonate are respectively in parts by weight: 1-5 parts of sodium lignosulphonate, 1-5 parts of carbon black and 2-15 parts of barium sulfate.
Most preferably, in the negative electrode expanding agent for the storage battery, the conductive material, the barium sulfate and the sodium lignosulfonate are respectively in parts by weight: 1-2 parts of sodium lignosulphonate, 1-2 parts of carbon black and 2-5 parts of barium sulfate.
The inventor of the invention finds in research that sodium lignosulfonate in the expanding agent plays an important role in the deep cycle life of the storage battery, and different selections of sodium lignosulfonate can lead to different deep cycle lives of the storage battery. The inventor shows through a large number of experimental studies that the modified sodium lignosulfonate obtained by reacting alkali lignin with p-chloromethyl styrene under the conditions of the invention and then carrying out sulfonation reaction can greatly prolong the deep cycle life of the storage battery compared with other sodium lignosulfonates.
The invention also provides a preparation method of the negative electrode expanding agent for the storage battery, which comprises the following steps:
(1) mixing a conductive material, barium sulfate and modified sodium lignosulfonate in a mixer;
(2) and then transferring the mixture into a ball mill for ball milling for 5-60 min to obtain the negative electrode expanding agent for the storage battery.
Preferably, the specific mixing method in the mixer in the step (1) is as follows: the conductive material and the modified sodium lignosulfonate are mixed for 10-20 min, and then the barium sulfate is added and mixed for 20-30 min.
The inventor finds that the mixing mode in the step (1) plays an important role in whether a uniformly dispersed and stable negative electrode expanding agent can be obtained or not in a specific production process; the dispersion and stability of specific negative electrode swelling agents further affect the deep cycle life of the battery. Researches show that the obtained negative electrode expanding agent with specific dispersity and stability can be beneficial to further prolonging the deep cycle life of the storage battery only by fully and uniformly mixing the conductive material and the modified sodium lignosulfonate and then adding the modified sodium lignosulfonate for full mixing. Compared with the negative electrode expanding agent obtained by directly mixing the conductive material, the barium sulfate and the modified lignosulfonic acid, the method is more beneficial to improving the deep cycle life.
Preferably, the mixer is selected from horizontal coulter mixers.
Preferably, the inner wall of the ball mill is made of stainless steel, polyurethane or a ceramic lining plate; the grinding medium in the ball mill is selected from metal balls and/or metal oxide ceramic balls.
Most preferably, the stainless steel is 304 stainless steel.
Preferably, the metal balls are selected from stainless steel balls; the metal oxide ceramic ball is selected from a zirconium dioxide ceramic ball or an aluminum oxide ceramic ball.
Most preferably, the stainless steel ball is a 304 stainless steel ball.
Preferably, the volume filling rate of the grinding media in the ball mill is 20-60%.
Preferably, the grinding media in the ball mill are graded by metal balls and/or metal oxide ceramic balls with three sizes; respectively are metal balls or metal oxide ceramic balls with the diameter of 2-15 mm; metal balls or metal oxide ceramic balls with the diameter of 15-50 mm; metal balls or metal oxide ceramic balls with a diameter of 50-100 mm.
More preferably, the weight ratio of the metal balls or metal oxide ceramic balls with the diameter of 2-15 mm to the metal balls or metal oxide ceramic balls with the diameter of 15-50 mm to the metal balls or metal oxide ceramic balls with the diameter of 50-100 mm is 1-50: 1-50: 1-50.
More preferably, the weight ratio of the metal balls or metal oxide ceramic balls with the diameter of 2-15 mm to the metal balls or metal oxide ceramic balls with the diameter of 15-50 mm to the metal balls or metal oxide ceramic balls with the diameter of 50-100 mm is 1-5: 1-5: 1-5.
Still more preferably, the grinding media in the ball mill are graded by using metal balls and/or metal oxide ceramic balls with three sizes; stainless steel balls with the diameter of 2-15 mm are respectively arranged; zirconium dioxide ceramic balls with the diameter of 15-50 mm; alumina ceramic balls with the diameter of 50-100 mm; the weight ratio of the stainless steel balls to the zirconium dioxide ceramic balls to the aluminum oxide ceramic balls is 3-5: 1-2: 1.
further, ball milling in the step (2) is carried out for 5-10 min by adopting a rotation rate of 85% -90%, then ball milling is carried out for 10-15 min by adjusting the rotation rate to 65% -70%, then ball milling is carried out for 5-10 min by adjusting the rotation rate to 80% -85%, and finally ball milling is carried out for 15-25 min by adjusting the rotation rate to 50% -60%.
The inventors found in the specific production process that the ball milling mode in step (2) also plays an important role in obtaining a uniformly dispersed and stable negative electrode expanding agent. Research shows that only by ball milling under the alternate change of different rotating speeds, the negative electrode expanding agent which has specific dispersity and stability and is beneficial to further prolonging the deep cycle life of the storage battery can be obtained. Compared with the negative electrode expanding agent directly obtained by ball milling at the same ball milling rotating speed, the deep cycle life of the storage battery can be prolonged.
Has the advantages that: the invention provides a storage battery cathode expanding agent containing brand-new modified sodium lignosulfonate; research shows that the storage battery cathode expanding agent added with brand-new modified sodium lignosulfonate can greatly prolong the deep cycle life of the storage battery. Further, in the preparation method, the inventor researches and discovers that the mixing mode in the mixer and the ball milling rotation speed rate in the ball mill can determine the dispersion degree and stability of the negative electrode expanding agent; research shows that the negative electrode expanding agent beneficial to further prolonging the deep cycle life of the storage battery can be obtained under the mixing and ball milling conditions.
Detailed Description
The present invention is further explained below with reference to specific examples, but the scope of protection of the present invention is not limited to the specific examples.
Example 1 preparation of negative electrode expander for secondary battery
The negative electrode expanding agent for the storage battery comprises the following raw materials in parts by weight: 1 part of sodium lignosulfonate, 1 part of carbon black (carbon black R425P, available from Angstroma chemical Co., Ltd., Guangzhou) and 5 parts of precipitated barium sulfate.
The sodium lignosulfonate is modified sodium lignosulfonate, and is prepared by the following method:
(1) adding wheat straw alkali lignin into 4 times of acidic aqueous solution with pH value of 3, stirring for 40min, filtering, and collecting precipitated alkali lignin;
(2) adding precipitated alkali lignin and p-chloromethyl styrene in a weight ratio of 2.5:1 into absolute ethyl alcohol (the weight of the absolute ethyl alcohol is 5 times of that of the precipitated alkali lignin), mixing, and reacting for 4 hours at 140 ℃; obtaining p-chloromethylstyrylation precipitation alkali lignin;
(3) adding p-chloromethylstyrenated precipitated alkali lignin into a sodium sulfite aqueous solution with the mass fraction of 25% and the weight of 4 times of that of the p-chloromethylstyrenated precipitated alkali lignin, adjusting the pH value to 13, reacting for 2.5 hours at the temperature of 140 ℃, and taking a product to obtain the modified sodium lignosulfonate.
The preparation method of the negative electrode expanding agent for the storage battery comprises the following steps: and (3) putting the modified sodium lignosulphonate, the carbon black and the precipitated barium sulfate into a horizontal coulter mixer to mix for 90min to obtain the modified sodium lignosulphonate.
Example 2 preparation of negative electrode expander for secondary battery
The composition of the raw materials was the same as in example 1.
The preparation method of the negative electrode expanding agent for the storage battery comprises the following steps:
(1) putting the modified sodium lignosulphonate, the carbon black and the precipitated barium sulfate into a horizontal coulter mixer for mixing for 30 min;
(2) then transferring the mixture into a ball mill to perform ball milling for 60min to obtain the negative electrode expanding agent for the storage battery; the rotation speed rate of the ball mill is 70 percent;
the inner wall of the ball mill is made of 304 stainless steel; the volume filling rate of the grinding medium in the ball mill is 45 percent; the grinding medium in the ball mill is graded by metal balls and metal oxide ceramic balls with three sizes; 304 stainless steel balls with the diameter of 10mm are respectively arranged; zirconium dioxide ceramic balls with the diameter of 25 mm; alumina ceramic balls with the diameter of 75 mm; the weight ratio of the stainless steel balls to the zirconium dioxide ceramic balls to the aluminum oxide ceramic balls is 4: 2: 1.
example 3 preparation of negative electrode expander for secondary battery
The composition of the raw materials was the same as in example 1.
The preparation method of the negative electrode expanding agent for the storage battery comprises the following steps:
(1) firstly, mixing a conductive material and modified sodium lignosulfonate for 10min, and then adding precipitated barium sulfate for mixing for 20 min;
(2) then transferring the mixture into a ball mill for ball milling; firstly, ball-milling for 10min at a rotation rate of 87%, then ball-milling for 15min at a rotation rate of 68%, then ball-milling for 10min at a rotation rate of 80%, and finally ball-milling for 25min at a rotation rate of 55%;
the inner wall of the ball mill is made of 304 stainless steel; the volume filling rate of the grinding medium in the ball mill is 45 percent; the grinding medium in the ball mill is graded by metal balls and metal oxide ceramic balls with three sizes; 304 stainless steel balls with the diameter of 10mm are respectively arranged; zirconium dioxide ceramic balls with the diameter of 25 mm; alumina ceramic balls with the diameter of 75 mm; the weight ratio of the stainless steel balls to the zirconium dioxide ceramic balls to the aluminum oxide ceramic balls is 4: 2: 1.
comparative example 1 preparation of negative electrode expander for secondary battery
The negative electrode expanding agent for the storage battery comprises the following raw materials in parts by weight: 1 part of sodium lignosulfonate, 1 part of carbon black (carbon black R425P, available from Angstroma chemical Co., Ltd., Guangzhou) and 5 parts of precipitated barium sulfate.
The sodium lignosulfonate is prepared by the following method:
(1) adding wheat straw alkali lignin into 4 times of acidic aqueous solution with pH value of 3, stirring for 40min, filtering, and collecting precipitated alkali lignin;
(3) adding the precipitated alkali lignin into a sodium sulfite aqueous solution with the mass fraction of 25% and the weight of 4 times of that of the sodium sulfite aqueous solution, adjusting the pH value to be 13, reacting for 2.5 hours at the temperature of 140 ℃, and taking the product to obtain the sodium lignosulphonate.
The preparation method of the negative electrode expanding agent for the storage battery comprises the following steps: and (3) putting the modified sodium lignosulphonate, the carbon black and the precipitated barium sulfate into a horizontal coulter mixer to mix for 90min to obtain the modified sodium lignosulphonate.
Comparative example 1 differs from example 1 in that the sodium lignosulfonate preparation step does not include a step of reacting precipitated alkali lignin with p-chloromethylstyrene.
Comparative example 2 preparation of negative electrode expander for secondary battery
The negative electrode expanding agent for the storage battery comprises the following raw materials in parts by weight: 1 part of sodium lignosulfonate, 1 part of carbon black (carbon black R425P, available from Angstroma chemical Co., Ltd., Guangzhou) and 5 parts of precipitated barium sulfate.
The sodium lignosulfonate is modified sodium lignosulfonate, and is prepared by the following method:
(1) adding wheat straw alkali lignin into 4 times of acidic aqueous solution with pH value of 3, stirring for 40min, filtering, and collecting precipitated alkali lignin;
(2) adding precipitated alkali lignin and 1-chlorooctadecane in a weight ratio of 2.5:1 into absolute ethyl alcohol (the amount of the absolute ethyl alcohol is 5 times of the weight of the precipitated alkali lignin), mixing, and reacting for 4 hours at 140 ℃; obtaining 1-chlorooctadecylated precipitated alkali lignin;
(3) adding 1-chlorooctadecanoic acid precipitated alkali lignin into a sodium sulfite aqueous solution with the mass fraction of 25% and the weight of 4 times of that of the sodium sulfite aqueous solution, adjusting the pH value to 13, reacting for 2.5 hours at the temperature of 140 ℃, and taking the product to obtain the modified sodium lignosulphonate.
The preparation method of the negative electrode expanding agent for the storage battery comprises the following steps: and (3) putting the modified sodium lignosulphonate, the carbon black and the precipitated barium sulfate into a horizontal coulter mixer to mix for 90min to obtain the modified sodium lignosulphonate.
Comparative example 2 differs from example 1 in that 1-chlorooctadecane was used to react with precipitated alkali lignin in step (2), whereas example 1 used p-chloromethylstyrene.
Comparative example 3 preparation of negative electrode expander for secondary battery
The composition of the raw materials was the same as in example 1.
The preparation method of the negative electrode expanding agent for the storage battery comprises the following steps:
(1) firstly, mixing a conductive material and modified sodium lignosulfonate for 10min, and then adding precipitated barium sulfate for mixing for 20 min;
(2) then transferring the mixture into a ball mill for ball milling; firstly, ball-milling for 10min at a rotation rate of 80%, then ball-milling for 15min at a rotation rate of 50%, then ball-milling for 10min at a rotation rate of 85%, and finally ball-milling for 25min at a rotation rate of 65%;
the inner wall of the ball mill is made of 304 stainless steel; the volume filling rate of the grinding medium in the ball mill is 45 percent; the grinding medium in the ball mill is graded by metal balls and metal oxide ceramic balls with three sizes; 304 stainless steel balls with the diameter of 10mm are respectively arranged; zirconium dioxide ceramic balls with the diameter of 25 mm; alumina ceramic balls with the diameter of 75 mm; the weight ratio of the stainless steel balls to the zirconium dioxide ceramic balls to the aluminum oxide ceramic balls is 4: 2: 1.
comparative example 3 is different from example 3 in the specific rotation rate conditions in the ball milling step.
Examples of the experiments
1kg of the negative electrode expanding agent for the storage battery prepared in the examples 1-3 and the comparative examples 1-3, 100kg of lead powder, 10.5kg of sulfuric acid (1.40g/m L) and 10kg of water are respectively added into a paste mixer to be mixed and pasted to obtain negative electrode lead paste, then the negative electrode lead paste is used for coating to obtain a negative plate, the negative plate is assembled into a 12V60Ah automobile starting battery according to a conventional method, the deep cycle life of the automobile starting battery is tested according to the GMW3092-2007 standard (the standard specifies that the deep cycle life must be longer than 7 24 charge-discharge cycles), and the concrete results are shown in Table 1.
TABLE 1 Effect of negative electrode swelling agents for different batteries on deep cycle life of automotive starting cells
| Deep cycle life of automotive starting battery | |
| Example 1 negative electrode expander for secondary battery | 14 24 charge-discharge cycles |
| EXAMPLE 2 negative electrode expander for Secondary Battery | 17 24 charge-discharge cycles |
| Example 3 negative electrode expander for storage batteries | 23 24 charge-discharge cycles |
| Comparative example 1 negative electrode expander for secondary battery | 10 24 charge-discharge cycles |
| Comparative example 2 negative electrode expander for secondary battery | 9 24 charge-discharge cycles |
| Comparative example 3 negative electrode expander for secondary battery | 19 24 charge-discharge cycles |
As can be seen from the data in Table 1, the deep cycle life of the automobile starting battery prepared from the negative electrode expanding agent for the storage battery prepared in the embodiments 1-3 is more than 17, and is far more than 7 specified by the standard; the cathode expanding agent for the storage battery can well prolong the deep cycle life of the starting battery of the automobile.
Compared with the comparative examples 1 and 2, the negative electrode expanding agent for the storage battery prepared in the example 1 has far longer deep cycle life on the automobile starting battery than the comparative examples 1 and 2; this demonstrates that the selection of lignosulfonic acid in negative electrode swelling agents for batteries plays a significant role in the deep cycle life of automotive starting batteries. The invention makes alkali lignin react with p-chloromethyl styrene under the condition of the invention, and then the modified sodium lignosulfonate obtained by sulfonation reaction can greatly improve the deep cycle life of the storage battery. The sodium lignosulphonate obtained by the alkali lignin which does not react with p-chloromethyl styrene or other substances cannot effectively prolong the deep cycle life of the storage battery.
In addition, in examples 1-3 and comparative example 3, the deep cycle life of the negative electrode expanding agent for the storage battery prepared in example 3 for the automobile starting battery is greatly improved in a range larger than that of examples 1 and 2 and comparative example 3, which shows that the deep cycle life of the automobile starting battery can be further improved by further adjusting the preparation method on the basis of adopting the modified sodium lignosulfonate; and the negative electrode expanding agent which is beneficial to further prolonging the deep cycle life of the storage battery can be obtained under the mixing and ball milling conditions.
Claims (10)
1. A negative electrode expanding agent for a storage battery comprises the following components: conductive materials, barium sulfate and sodium lignosulfonate; it is characterized in that the preparation method is characterized in that,
the sodium lignosulfonate is modified sodium lignosulfonate, and is prepared by the following method:
(1) adding alkali lignin into an acidic aqueous solution, stirring, filtering, and taking precipitated alkali lignin;
(2) adding the precipitated alkali lignin and p-chloromethyl styrene into an organic solvent, mixing, and reacting for 3-5 h at 130-150 ℃; obtaining p-chloromethylstyrylation precipitation alkali lignin;
(3) adding p-chloromethylstyrenated precipitated alkali lignin into an aqueous solution containing sodium sulfite, adjusting the pH value to 13-14, reacting for 2-3 h at 130-150 ℃, and taking the product to obtain the modified sodium lignosulfonate.
2. The negative electrode additive for a secondary battery according to claim 1, wherein the acidic aqueous solution in the step (1) is an acidic aqueous solution having a pH of 2 to 3; the dosage of the acidic aqueous solution is 3-5 times of that of the alkali lignin; most preferably, the acidic aqueous solution in step (1) is an acidic aqueous solution with a pH value of 3; the dosage of the acidic aqueous solution is 4 times of that of the alkali lignin.
3. The negative electrode expander for a storage battery as claimed in claim 1, wherein the alkali lignin in step (1) is wheat straw alkali lignin.
4. The negative electrode expanding agent for the storage battery as claimed in claim 1, wherein the weight ratio of the precipitated alkali lignin to the p-chloromethyl styrene in the step (2) is 2-3: 1; most preferably, the weight ratio of precipitated alkali lignin to p-chloromethylstyrene in step (2) is 2.5: 1.
5. The negative electrode expander for secondary batteries according to claim 1, wherein the organic solvent in the step (2) is ethanol.
6. The negative electrode additive for secondary batteries according to claim 1, wherein the reaction in step (2) is carried out at 140 ℃ for 4 hours.
7. The negative electrode expanding agent for the storage battery as claimed in claim 1, wherein the mass fraction of the aqueous solution of sodium sulfite in the step (3) is 20 to 30%; the weight of the aqueous solution containing sodium sulfite is 3-5 times of the weight of the p-chloromethylstyrylation precipitation alkali lignin.
8. The negative electrode expander for a secondary battery as claimed in claim 1, wherein the conductive material is one or a mixture of two or more selected from carbon black, carbon nanotubes and graphene; the barium sulfate is selected from precipitated barium sulfate.
9. The negative electrode expander for storage batteries according to claim 1, wherein the conductive material, barium sulfate and sodium lignosulfonate are in parts by weight: 1-5 parts of sodium lignosulphonate, 1-5 parts of carbon black and 2-15 parts of barium sulfate.
10. The negative electrode expander for storage batteries according to claim 1, wherein the conductive material, barium sulfate and sodium lignosulfonate are in parts by weight: 1-2 parts of sodium lignosulphonate, 1-2 parts of carbon black and 2-5 parts of barium sulfate.
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| CN113224394A (en) * | 2021-04-20 | 2021-08-06 | 淄博火炬能源有限责任公司 | Low-temperature lead-carbon battery electrolyte |
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| CN102088088A (en) * | 2010-12-06 | 2011-06-08 | 山东圣阳电源科技有限公司 | Cathode diachylon used for power-type lead-acid storage battery and manufacture method thereof |
| CN103384004A (en) * | 2013-07-05 | 2013-11-06 | 超威电源有限公司 | Storage battery cathode formula and preparation technology thereof |
| CN107265904A (en) * | 2017-06-07 | 2017-10-20 | 常州市丰瑞电子有限公司 | A kind of preparation method of the composite sulfonated water reducer of lignin/starch base |
| CN108598472A (en) * | 2018-03-15 | 2018-09-28 | 天能电池集团有限公司 | A kind of low temperature resistant lead accumulator cathode lead plaster and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113224394A (en) * | 2021-04-20 | 2021-08-06 | 淄博火炬能源有限责任公司 | Low-temperature lead-carbon battery electrolyte |
| CN113224394B (en) * | 2021-04-20 | 2022-05-03 | 淄博火炬能源有限责任公司 | Low-temperature lead-carbon battery electrolyte |
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Effective date of registration: 20211201 Address after: 510000 room 106, building G7, South China new material innovation park, building 2, No. 31, Kefeng Road, Guangzhou high tech Industrial Development Zone, Guangzhou, Guangdong Province Patentee after: Guangzhou Edenta Chemical Co.,Ltd. Address before: 313100 Chengnan Industrial Park, Heping Town, Changxing County, Huzhou City, Zhejiang Province Patentee before: Zhejiang erdenda new energy materials Co.,Ltd. |