CN111403680A - Preparation method of negative electrode expanding agent for storage battery - Google Patents
Preparation method of negative electrode expanding agent for storage battery Download PDFInfo
- Publication number
- CN111403680A CN111403680A CN202010163013.6A CN202010163013A CN111403680A CN 111403680 A CN111403680 A CN 111403680A CN 202010163013 A CN202010163013 A CN 202010163013A CN 111403680 A CN111403680 A CN 111403680A
- Authority
- CN
- China
- Prior art keywords
- preparation
- balls
- mixing
- negative electrode
- ball milling
- 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.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of battery additive preparation, and particularly discloses a preparation method of a negative electrode expanding agent for a storage battery. The preparation method comprises the following steps: (1) mixing a conductive material, barium sulfate and sodium lignosulfonate in a mixer; (2) 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; the specific mixing method in the mixer in the step (1) comprises the following steps: firstly, mixing a conductive material and sodium lignosulphonate for 10-20 min, and then adding barium sulfate for mixing for 20-30 min. The negative electrode expanding agent for the storage battery prepared by the method 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 preparation method of 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 preparation method of a negative electrode expanding agent for a storage battery. The negative electrode expanding agent for the storage battery prepared by the method 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:
(1) mixing a conductive material, barium sulfate and 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: firstly, mixing a conductive material and sodium lignosulphonate for 10-20 min, and then adding barium sulfate for mixing 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.
Preferably, the sodium lignosulfonate is modified sodium lignosulfonate, and the modified sodium lignosulfonate 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 the sodium lignosulfonate in the expanding agent also plays an important role in the deep cycle life of the storage battery, and the different selections of the 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.
Has the advantages that: the invention provides a brand-new preparation method of a storage battery expanding agent, and the inventor researches and discovers that the dispersion degree and the stability of a negative electrode expanding agent can be determined by a mixing mode in a mixer and the ball milling rotation speed ratio in a ball mill; 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. Furthermore, the invention also provides a storage battery cathode expanding agent containing brand new modified sodium lignosulphonate in the preparation method; 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.
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:
(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 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: 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 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.
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.
Comparative example 4 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 4 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 5 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 5 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.
Examples of the experiments
1kg of the negative electrode expanding agent for the storage battery prepared in the example 1 and the comparative examples 1-5, 100kg of lead powder, 10.5kg of sulfuric acid (1.40g/m L) and 10kg of water are respectively added into a paste mixing machine for mixing and pasting 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 stipulates that the deep cycle life must be longer than 7 24 charge-discharge cycles), and the specific test result is 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 | 23 24 charge-discharge cycles |
| Comparative example 1 negative electrode expander for secondary battery | 14 24 charge-discharge cycles |
| Comparative example 2 negative electrode expander for secondary battery | 17 24 charge-discharge cycles |
| Comparative example 3 negative electrode expander for secondary battery | 19 24 charge-discharge cycles |
| Comparative example 4 negative electrode expander for secondary battery | 10 24 charge-discharge cycles |
| Comparative example 5 negative electrode expander for secondary battery | 9 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 in example 1 is 23, which is far more than 7 specified by the standard; the negative electrode expanding agent for the storage battery prepared by the method can well prolong the deep cycle life of the automobile starting battery.
In addition, in the embodiment 1 and the comparative examples 1 to 3, the deep cycle life of the automobile starting battery is greatly improved by the negative electrode expanding agent for the storage battery prepared in the embodiment 1, which is far greater than that of the comparative examples 1 to 3, and this shows that the preparation method of the negative electrode expanding agent for the storage battery has an important influence on the improvement of the deep cycle life of the automobile starting battery; in the step (1), the negative electrode expanding agent with specific dispersity and stability, which is obtained by performing ball milling under the alternative conversion of different rotating speeds in the step (2), can be beneficial to improving the deep cycle life of the storage battery only after fully mixing the conductive material and the modified sodium lignosulfonate, then adding the modified sodium lignosulfonate and fully mixing.
Compared with comparative example 1, the negative electrode expanding agent for the storage battery prepared in comparative example 1 has far longer deep cycle life for the automobile starting battery than that of comparative examples 4 and 5; 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.
Claims (10)
1. A preparation method of a negative electrode expanding agent for a storage battery is characterized by comprising the following steps:
(1) mixing a conductive material, barium sulfate and sodium lignosulfonate in a mixer;
(2) 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;
the specific mixing method in the mixer in the step (1) comprises the following steps: firstly, mixing a conductive material and sodium lignosulphonate for 10-20 min, and then adding barium sulfate for mixing for 20-30 min.
2. The production method according to claim 1,
the specific mixing method in the mixer in the step (1) comprises the following steps: firstly, mixing the conductive material and sodium lignosulphonate for 10min, and then adding barium sulfate for mixing for 20 min.
3. The preparation method according to claim 1, wherein the ball milling in the step (2) is performed by ball milling at a rotation rate of 85-90%, then ball milling at a rotation rate of 65-70%, then ball milling at a rotation rate of 80-85%, and finally ball milling at a rotation rate of 50-60%.
4. The preparation method according to claim 3, wherein the ball milling in the step (2) is performed by ball milling at a rotation rate of 85-90% for 5-10 min, adjusting the rotation rate to 65-70% for ball milling for 10-15 min, adjusting the rotation rate to 80-85% for ball milling for 5-10 min, and adjusting the rotation rate to 50-60% for ball milling for 15-25 min.
5. The preparation method according to claim 1, wherein the ball mill in the step (2) has an inner wall made of stainless steel, polyurethane or ceramic lining plate; the grinding medium in the ball mill is selected from metal balls and/or metal oxide ceramic balls.
6. The method of claim 5, wherein the metal balls are selected from the group consisting of stainless steel balls; the metal oxide ceramic ball is selected from a zirconium dioxide ceramic ball or an aluminum oxide ceramic ball.
7. The preparation method according to claim 6, wherein the grinding media in the ball mill are graded by selecting 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.
8. The method according to claim 1, wherein the sodium lignosulfonate is a modified sodium lignosulfonate, and the modified sodium lignosulfonate is prepared by the following steps:
(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.
9. The preparation method according to 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.
10. The preparation method according to claim 1, wherein 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010163013.6A CN111403680B (en) | 2020-03-10 | 2020-03-10 | Preparation method of negative electrode expanding agent for storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010163013.6A CN111403680B (en) | 2020-03-10 | 2020-03-10 | Preparation method of negative electrode expanding agent for storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111403680A true CN111403680A (en) | 2020-07-10 |
| CN111403680B CN111403680B (en) | 2021-07-06 |
Family
ID=71432327
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010163013.6A Active CN111403680B (en) | 2020-03-10 | 2020-03-10 | Preparation method of negative electrode expanding agent for storage battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111403680B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117038994A (en) * | 2023-09-13 | 2023-11-10 | 广州埃登达化工有限公司 | Negative electrode expanding agent for storage battery |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101161347A (en) * | 2006-10-13 | 2008-04-16 | 南京理工大学 | Bidirectional tosh grinding ultra-fine crashing objects and its method |
| CN101173107A (en) * | 2007-10-23 | 2008-05-07 | 福州大学 | Raw material prescription for xylogen-inorganic nano composite material producing process thereof |
| CN101937991A (en) * | 2010-05-07 | 2011-01-05 | 张家口保胜新能源科技有限公司 | High-energy lead-acid storage battery cathode plate diachylon and preparation method thereof |
| CN102299337A (en) * | 2011-07-26 | 2011-12-28 | 山东金科力电源科技有限公司 | Composite additive to negative electrodes for lead acid batteries, preparation method and application method thereof |
| CN103247783A (en) * | 2013-04-10 | 2013-08-14 | 陕西凌云蓄电池有限责任公司 | Adding method of carbon black for lead-acid battery |
| CN104530444A (en) * | 2014-11-21 | 2015-04-22 | 东北林业大学 | Modification method for improving industrial lignin activity |
| CN108134054A (en) * | 2017-07-25 | 2018-06-08 | 骆驼集团襄阳蓄电池有限公司 | A kind of high-performance start and stop negative plate lead plaster and the application in lead-acid battery cathode plate |
-
2020
- 2020-03-10 CN CN202010163013.6A patent/CN111403680B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101161347A (en) * | 2006-10-13 | 2008-04-16 | 南京理工大学 | Bidirectional tosh grinding ultra-fine crashing objects and its method |
| CN101173107A (en) * | 2007-10-23 | 2008-05-07 | 福州大学 | Raw material prescription for xylogen-inorganic nano composite material producing process thereof |
| CN101937991A (en) * | 2010-05-07 | 2011-01-05 | 张家口保胜新能源科技有限公司 | High-energy lead-acid storage battery cathode plate diachylon and preparation method thereof |
| CN102299337A (en) * | 2011-07-26 | 2011-12-28 | 山东金科力电源科技有限公司 | Composite additive to negative electrodes for lead acid batteries, preparation method and application method thereof |
| CN103247783A (en) * | 2013-04-10 | 2013-08-14 | 陕西凌云蓄电池有限责任公司 | Adding method of carbon black for lead-acid battery |
| CN104530444A (en) * | 2014-11-21 | 2015-04-22 | 东北林业大学 | Modification method for improving industrial lignin activity |
| CN108134054A (en) * | 2017-07-25 | 2018-06-08 | 骆驼集团襄阳蓄电池有限公司 | A kind of high-performance start and stop negative plate lead plaster and the application in lead-acid battery cathode plate |
Non-Patent Citations (1)
| Title |
|---|
| D.P.BODEN等: "Comparison of methods for adding expander to lead-acid battery plates-advantage and disadvantage", 《JOURNAL OF POWER SOURCES》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117038994A (en) * | 2023-09-13 | 2023-11-10 | 广州埃登达化工有限公司 | Negative electrode expanding agent for storage battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111403680B (en) | 2021-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7377897B2 (en) | Preparation method and use of high viscosity carboxymethyl cellulose lithium | |
| CN1956244A (en) | Preparation method of plus plate material Li-Ni-Mn-Co-O of lithium ion battery | |
| CN107785549B (en) | Preparation method of carbon composite negative electrode material and carbon composite negative electrode material | |
| EP4283723A1 (en) | Coated ternary anode material, preparation method therefor, and lithium ion battery | |
| CN109449429B (en) | Lithium iron phosphate/silicon carbide composite material and preparation method thereof | |
| CN111403680B (en) | Preparation method of negative electrode expanding agent for storage battery | |
| CN109786714B (en) | Preparation method of mixed positive electrode slurry based on lithium manganate material | |
| CN111403681B (en) | Negative electrode expanding agent for storage battery | |
| CN109148878A (en) | A kind of method, positive electrode and lithium ion battery handling the residual lithium in surface containing lithium anode material | |
| CN108123132A (en) | Anode material of lithium battery and preparation method thereof, lithium battery anode and lithium battery | |
| GB2616231A (en) | Method for preparing graphene-based sodium ion battery negative electrode material | |
| CN116730317A (en) | Preparation method of lithium iron phosphate | |
| CN109755518B (en) | Preparation method of carbon-coated lithium iron phosphate material | |
| CN111392731A (en) | Preparation method of nano silica sand mill by taking polyvinylpyrrolidone as dispersing agent | |
| KR20220136293A (en) | Ternary cathode material of large-grained assembly, preparation method therefor, and lithium ion battery | |
| CN108695510A (en) | A kind of preparation method of stannic selenide composite negative pole material | |
| CN105742578B (en) | A kind of nickel-hydrogen battery negative pole slurry preparation method of addition carbon nanotube | |
| CN110289395B (en) | Paste for cathode of zinc-nickel battery and preparation method thereof | |
| CN103762355A (en) | Method for synthesizing lithium, nickel, manganese and cobalt composite oxide powder material | |
| CN111063874B (en) | Preparation method and application of hard carbon nano material for ion battery | |
| CN113745517A (en) | Preparation method of conductive paste | |
| CN111342043B (en) | Starting battery cathode material and preparation method thereof | |
| CN111403737A (en) | Negative electrode additive composition for lead-acid battery and preparation method thereof | |
| CN114605457B (en) | Preparation method of lithium bisoxalato borate | |
| CN113871623B (en) | High-nickel anode material slurry for lithium ion battery, preparation method of slurry and lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CB03 | Change of inventor or designer information |
Inventor after: Li Zhibin Inventor after: Pan Dong Inventor before: Li Zhibin |
|
| CB03 | Change of inventor or designer information |