CN117038994A - Negative electrode expanding agent for storage battery - Google Patents
Negative electrode expanding agent for storage battery Download PDFInfo
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- CN117038994A CN117038994A CN202311179966.1A CN202311179966A CN117038994A CN 117038994 A CN117038994 A CN 117038994A CN 202311179966 A CN202311179966 A CN 202311179966A CN 117038994 A CN117038994 A CN 117038994A
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- negative electrode
- barium sulfate
- lignin sulfonate
- sodium lignin
- expanding agent
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- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 154
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 100
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 98
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 97
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 97
- 238000002156 mixing Methods 0.000 claims abstract description 85
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 claims abstract description 78
- 239000006229 carbon black Substances 0.000 claims abstract description 71
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 238000000498 ball milling Methods 0.000 claims abstract description 21
- 230000008961 swelling Effects 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 6
- 239000002109 single walled nanotube Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 abstract description 19
- 239000004744 fabric Substances 0.000 abstract 2
- 239000000017 hydrogel Substances 0.000 abstract 2
- 239000002994 raw material Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000000981 high-pressure carbon monoxide method Methods 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/627—Expanders for 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
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application provides a negative electrode expanding agent for a storage battery, which comprises sodium lignin sulfonate, carbon black, carbon nanotubes and barium sulfate, wherein the mass ratio of the sodium lignin sulfonate to the barium sulfate is 1:4-1:4.5. The preparation method of the anode expanding agent comprises the following steps: (1) Firstly, mixing carbon black, carbon nano tubes, barium sulfate and sodium lignin sulfonate in a mixer; (2) Then transferring the mixture into a ball mill for ball milling for 30min to obtain the negative electrode expanding agent for the storage battery; the specific mixing method in the mixer in the step (1) is as follows: firstly mixing carbon black, carbon nano tube and sodium lignin sulfonate for 9min, then adding barium sulfate for mixing for 15min. Also comprises a hydrogel layer and a supporting cloth layer. Also comprises a hydrogel layer and a supporting cloth layer. The negative electrode expanding agent for the storage battery can effectively improve the cycle performance of the battery and has better low-temperature performance.
Description
Technical Field
The application belongs to the technical field of lead-acid batteries, and particularly relates to a negative electrode expanding agent for a storage battery.
Background
The lead-carbon battery has the advantages of higher energy ratio, safety, reliability, low price, high power, long cycle life and the like, and is widely applied to the fields of electric automobiles and the like, and carbon materials and lignin are indispensable parts in a negative plate of the lead-carbon battery. The sodium lignin sulfonate is used as an organic expanding agent, so that the shrinkage of the surface of the negative electrode lead and the passivation of the negative electrode lead sulfate in a low-temperature environment can be prevented, and the low-temperature performance of the battery can be effectively improved. The carbon material has good specific surface area, porosity, conductivity and the like, and can increase the specific surface area of the anode active material when being added into the anode, improve the utilization rate of the active material under a high-rate charge state, absorb the overcharge current to inhibit anode sulfation, and prolong the service life of the battery.
For example, the inventor optimizes the preparation method of the negative electrode expanding agent for the storage battery with the patent number ZL202010163639.7 to ensure that the conductive material, the barium sulfate and the sodium lignin sulfonate are well mixed, thereby improving the circulation, but the low-temperature performance of the negative electrode expanding agent is poor.
For this reason, we propose a negative electrode swelling agent for a secondary battery to solve the above-mentioned problems.
Disclosure of Invention
The application provides a negative electrode expanding agent for a storage battery, which can effectively improve the cycle performance of the battery and has better low-temperature performance.
The application provides a negative electrode expanding agent for a storage battery, which comprises sodium lignin sulfonate, carbon black, carbon nanotubes and barium sulfate, wherein the mass ratio of the sodium lignin sulfonate to the barium sulfate is 1:4-1:4.5.
In some embodiments, the negative electrode expansion agent is prepared by:
(1) Firstly, mixing carbon black, carbon nano tubes, barium sulfate and sodium lignin sulfonate in a mixer;
(2) Then transferring the mixture into a ball mill for ball milling for 30min to obtain the negative electrode expanding agent for the storage battery;
the specific mixing method in the mixer in the step (1) is as follows: firstly mixing carbon black, carbon nano tube and sodium lignin sulfonate for 9min, then adding barium sulfate for mixing for 15min.
In some embodiments, the mass ratio of sodium lignin sulfonate to barium sulfate is 1:4.2 to 1:4.5.
In some embodiments, the carbon nanotubes have a length of 1.0 to 1.5 μm.
In some embodiments, the mass of the carbon nanotubes is 1% -2% based on the total mass of the negative electrode expansion agent.
In some embodiments, the carbon nanotubes have a specific surface area of 100m 2 /g-200m 2 /g。
In some embodiments, the carbon nanotubes have a tube diameter of 4nm to 4.5nm.
In some embodiments, the carbon nanotubes are single-walled carbon nanotubes.
In some embodiments, the carbon black has a particle size of 0.05 to 10 μm.
In some embodiments, the carbon black has a particle size of 4 to 5 μm.
The negative electrode expanding agent for the storage battery comprises sodium lignin sulfonate, carbon black, carbon nanotubes and barium sulfate, wherein the mass ratio of the sodium lignin sulfonate to the barium sulfate is 1:4-1:4.5. The battery cycle performance can be effectively improved, and the battery has better low-temperature performance.
Detailed Description
The following description of the embodiments of the present application will clearly and fully describe the technical solutions of the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
The application provides a negative electrode expanding agent for a storage battery, which comprises sodium lignin sulfonate, carbon black, carbon nanotubes and barium sulfate, wherein the mass ratio of the sodium lignin sulfonate to the barium sulfate is 1:4-1:4.5. Sodium lignin sulfonate and barium sulfate are commercially available conventional materials.
In some embodiments, the negative electrode expansion agent is prepared by:
(1) Firstly, mixing carbon black, carbon nano tubes, barium sulfate and sodium lignin sulfonate in a mixer;
(2) Then transferring the mixture into a ball mill for ball milling for 30min to obtain the negative electrode expanding agent for the storage battery;
the specific mixing method in the mixer in the step (1) is as follows: firstly mixing carbon black, carbon nano tube and sodium lignin sulfonate for 9min, then adding barium sulfate for mixing for 15min.
In some embodiments, the mass ratio of sodium lignin sulfonate to barium sulfate is 1:4.2 to 1:4.5.
In some embodiments, the carbon nanotubes have a length of 1.0 to 1.5 μm.
In some embodiments, the mass of the carbon nanotubes is 1% -2% based on the total mass of the negative electrode expansion agent.
In some embodiments, the carbon nanotubes have a specific surface area of 100m 2 /g-200m 2 /g。
In some embodiments, the carbon nanotubes have a tube diameter of 4nm to 4.5nm.
In some embodiments, the carbon nanotubes are single-walled carbon nanotubes.
In some embodiments, the carbon black has a particle size of 0.05 to 10 μm.
In some embodiments, the carbon black has a particle size of 4 to 5 μm.
Carbon nanotubes purified HiPco single-walled carbon nanotubes were selected and purchased from carbon nanofabrication company. Carbon black is conductive carbon black SP, purchased from hualiuan.
Example 1:
the anode expanding agent for the storage battery comprises the following raw materials in parts by weight: 1 part of sodium lignin sulfonate, 1 part of carbon black and 4 parts of barium sulfate, and 0.5% of carbon nano tube based on the total mass of the anode expanding agent is added. The preparation method of the anode expanding agent comprises the following steps:
(1) Firstly, mixing carbon black, carbon nano tubes, barium sulfate and sodium lignin sulfonate in a mixer;
(2) Then transferring the mixture into a ball mill for ball milling for 30min to obtain the negative electrode expanding agent for the storage battery;
the specific mixing method in the mixer in the step (1) is as follows: firstly mixing carbon black, carbon nano tube and sodium lignin sulfonate for 9min, then adding barium sulfate for mixing for 15min.
Example 2:
the anode expanding agent for the storage battery comprises the following raw materials in parts by weight: 1 part of sodium lignin sulfonate, 1 part of carbon black and 4.2 parts of barium sulfate, and 0.5% of carbon nano tube based on the total mass of the anode expanding agent is added. The preparation method of the anode expanding agent comprises the following steps:
(1) Firstly, mixing carbon black, carbon nano tubes, barium sulfate and sodium lignin sulfonate in a mixer;
(2) Then transferring the mixture into a ball mill for ball milling for 30min to obtain the negative electrode expanding agent for the storage battery;
the specific mixing method in the mixer in the step (1) is as follows: firstly mixing carbon black, carbon nano tube and sodium lignin sulfonate for 9min, then adding barium sulfate for mixing for 15min.
Example 3:
the anode expanding agent for the storage battery comprises the following raw materials in parts by weight: 1 part of sodium lignin sulfonate, 1 part of carbon black and 4.4 parts of barium sulfate, and 0.5% of carbon nano tube based on the total mass of the anode expanding agent is added. The preparation method of the anode expanding agent comprises the following steps:
(1) Firstly, mixing carbon black, carbon nano tubes, barium sulfate and sodium lignin sulfonate in a mixer;
(2) Then transferring the mixture into a ball mill for ball milling for 30min to obtain the negative electrode expanding agent for the storage battery;
the specific mixing method in the mixer in the step (1) is as follows: firstly mixing carbon black, carbon nano tube and sodium lignin sulfonate for 9min, then adding barium sulfate for mixing for 15min.
Example 4:
the anode expanding agent for the storage battery comprises the following raw materials in parts by weight: 1 part of sodium lignin sulfonate, 1 part of carbon black and 4.5 parts of barium sulfate, and 0.5% of carbon nano tube based on the total mass of the anode expanding agent is added. The preparation method of the anode expanding agent comprises the following steps:
(1) Firstly, mixing carbon black, carbon nano tubes, barium sulfate and sodium lignin sulfonate in a mixer;
(2) Then transferring the mixture into a ball mill for ball milling for 30min to obtain the negative electrode expanding agent for the storage battery;
the specific mixing method in the mixer in the step (1) is as follows: firstly mixing carbon black, carbon nano tube and sodium lignin sulfonate for 9min, then adding barium sulfate for mixing for 15min.
Comparative example 1:
the anode expanding agent for the storage battery comprises the following raw materials in parts by weight: 1 part of sodium lignin sulfonate, 1 part of carbon black and 3 parts of barium sulfate, and 0.5% of carbon nano tube based on the total mass of the anode expanding agent is added. The preparation method of the anode expanding agent comprises the following steps:
(1) Firstly, mixing carbon black, carbon nano tubes, barium sulfate and sodium lignin sulfonate in a mixer;
(2) Then transferring the mixture into a ball mill for ball milling for 30min to obtain the negative electrode expanding agent for the storage battery;
the specific mixing method in the mixer in the step (1) is as follows: firstly mixing carbon black, carbon nano tube and sodium lignin sulfonate for 9min, then adding barium sulfate for mixing for 15min.
Comparative example 2:
the anode expanding agent for the storage battery comprises the following raw materials in parts by weight: 1 part of sodium lignin sulfonate, 1 part of carbon black and 5 parts of barium sulfate, and 0.5% of carbon nano tube based on the total mass of the anode expanding agent is added. The preparation method of the anode expanding agent comprises the following steps:
(1) Firstly, mixing carbon black, carbon nano tubes, barium sulfate and sodium lignin sulfonate in a mixer;
(2) Then transferring the mixture into a ball mill for ball milling for 30min to obtain the negative electrode expanding agent for the storage battery;
the specific mixing method in the mixer in the step (1) is as follows: firstly mixing carbon black, carbon nano tube and sodium lignin sulfonate for 9min, then adding barium sulfate for mixing for 15min.
Respectively taking 1kg of the anode swelling agent for the storage battery, 100kg of lead powder, 10.5kg of sulfuric acid (1.40 g/mL) and 10kg of water, which are prepared in the examples 1-3 and the comparative examples 1-2, adding the mixture into a paste mixing machine to mix the mixture to obtain anode lead paste, and then coating the anode lead paste to obtain a negative plate; the negative plate is then assembled into a 12V60Ah automobile starting battery according to the conventional method, and the deep cycle life of the automobile starting battery is tested with reference to the GMW3092-2007 standard (the standard prescribes that the deep cycle life must be greater than 7 24 charge and discharge cycles)
Wherein the length of the carbon nanotubes in examples 1 to 4 and comparative examples 1 to 2 was 1.0. Mu.m.
The test is carried out according to the national standard GB/T26826-2011 (measuring method of carbon nanotube diameter).
Specific surface area test:
the test was carried out according to the national standard GBT 19587-2017 (determination of specific surface area of solid substances by gas adsorption BET method).
The test is carried out according to the national standard GB/T26826-2011 (measuring method of carbon nanotube diameter).
The low-temperature capacity test method comprises the following steps: the fully charged battery was placed in a low temperature box at-20 c for 20h, then directly subjected to 3h rate capacity detection at-20 c with a discharge current of 63.3A and a termination voltage of 1.68V, the discharge capacity at low temperature was recorded, and the percentage of the low temperature capacity to the rated capacity was calculated.
Table 1: cycle life comparison of example 1-example 4 and comparative example 1-comparative example 2:
| example | Cycle life (cycle of secondary charge and discharge) | Low temperature capacity at-20 DEG C |
| Example 1 | 21 | 82％ |
| Example 2 | 22 | 83％ |
| Example 3 | 23 | 86％ |
| Example 4 | 24 | 87％ |
| Comparative example 1 | 15 | 74％ |
| Comparative example 2 | 20 | 78％ |
By the above table analysis, examples 1 to 4 have better cycle life than comparative examples 1 to 2, indicating that the mass ratio of sodium lignin sulfonate and barium sulfate is 1:4 to 1:4.5, and the possible reason is that the performance is effectively improved by defining the mass ratio of sodium lignin sulfonate and barium sulfate. And has better low-temperature performance.
Based on example 2, we further adjusted the length of the carbon nanotubes. The following examples are specifically made.
Example 5:
the anode expanding agent for the storage battery comprises the following raw materials in parts by weight: 1 part of sodium lignin sulfonate, 1 part of carbon black and 4.2 parts of barium sulfate, and 1% of carbon nano tube based on the total mass of the negative electrode expanding agent is added, wherein the length of the carbon nano tube is 1.0 mu m. The preparation method of the anode expanding agent comprises the following steps:
(1) Firstly, mixing carbon black, carbon nano tubes, barium sulfate and sodium lignin sulfonate in a mixer;
(2) Then transferring the mixture into a ball mill for ball milling for 30min to obtain the negative electrode expanding agent for the storage battery;
the specific mixing method in the mixer in the step (1) is as follows: firstly mixing carbon black, carbon nano tube and sodium lignin sulfonate for 9min, then adding barium sulfate for mixing for 15min.
Example 6:
the anode expanding agent for the storage battery comprises the following raw materials in parts by weight: 1 part of sodium lignin sulfonate, 1 part of carbon black and 4.2 parts of barium sulfate, and 1.2% of carbon nano tube based on the total mass of the anode expanding agent is added, wherein the length of the carbon nano tube is 1.0 mu m. The preparation method of the anode expanding agent comprises the following steps:
(1) Firstly, mixing carbon black, carbon nano tubes, barium sulfate and sodium lignin sulfonate in a mixer;
(2) Then transferring the mixture into a ball mill for ball milling for 30min to obtain the negative electrode expanding agent for the storage battery;
the specific mixing method in the mixer in the step (1) is as follows: firstly mixing carbon black, carbon nano tube and sodium lignin sulfonate for 9min, then adding barium sulfate for mixing for 15min.
Example 7:
the anode expanding agent for the storage battery comprises the following raw materials in parts by weight: 1 part of sodium lignin sulfonate, 1 part of carbon black and 4.2 parts of barium sulfate, and 1.3% of carbon nano tube based on the total mass of the anode expanding agent is added, wherein the length of the carbon nano tube is 1.0 mu m. The preparation method of the anode expanding agent comprises the following steps:
(1) Firstly, mixing carbon black, carbon nano tubes, barium sulfate and sodium lignin sulfonate in a mixer;
(2) Then transferring the mixture into a ball mill for ball milling for 30min to obtain the negative electrode expanding agent for the storage battery;
the specific mixing method in the mixer in the step (1) is as follows: firstly mixing carbon black, carbon nano tube and sodium lignin sulfonate for 9min, then adding barium sulfate for mixing for 15min.
Example 8:
the anode expanding agent for the storage battery comprises the following raw materials in parts by weight: 1 part of sodium lignin sulfonate, 1 part of carbon black and 4.2 parts of barium sulfate, and 1.4% of carbon nano tube based on the total mass of the anode expanding agent is added, wherein the length of the carbon nano tube is 1.0 mu m. The preparation method of the anode expanding agent comprises the following steps:
(1) Firstly, mixing carbon black, carbon nano tubes, barium sulfate and sodium lignin sulfonate in a mixer;
(2) Then transferring the mixture into a ball mill for ball milling for 30min to obtain the negative electrode expanding agent for the storage battery;
the specific mixing method in the mixer in the step (1) is as follows: firstly mixing carbon black, carbon nano tube and sodium lignin sulfonate for 9min, then adding barium sulfate for mixing for 15min.
Example 9:
the anode expanding agent for the storage battery comprises the following raw materials in parts by weight: 1 part of sodium lignin sulfonate, 1 part of carbon black and 4.2 parts of barium sulfate, and 1.5% of carbon nano tube based on the total mass of the anode expanding agent is added, wherein the length of the carbon nano tube is 1.0 mu m. The preparation method of the anode expanding agent comprises the following steps:
(1) Firstly, mixing carbon black, carbon nano tubes, barium sulfate and sodium lignin sulfonate in a mixer;
(2) Then transferring the mixture into a ball mill for ball milling for 30min to obtain the negative electrode expanding agent for the storage battery;
the specific mixing method in the mixer in the step (1) is as follows: firstly mixing carbon black, carbon nano tube and sodium lignin sulfonate for 9min, then adding barium sulfate for mixing for 15min.
Example 10:
the anode expanding agent for the storage battery comprises the following raw materials in parts by weight: 1 part of sodium lignin sulfonate, 1 part of carbon black and 4.2 parts of barium sulfate, and 1.6% of carbon nano tube based on the total mass of the anode expanding agent is added, wherein the length of the carbon nano tube is 1.0 mu m. The preparation method of the anode expanding agent comprises the following steps:
(1) Firstly, mixing carbon black, carbon nano tubes, barium sulfate and sodium lignin sulfonate in a mixer;
(2) Then transferring the mixture into a ball mill for ball milling for 30min to obtain the negative electrode expanding agent for the storage battery;
the specific mixing method in the mixer in the step (1) is as follows: firstly mixing carbon black, carbon nano tube and sodium lignin sulfonate for 9min, then adding barium sulfate for mixing for 15min.
Example 11:
the anode expanding agent for the storage battery comprises the following raw materials in parts by weight: 1 part of sodium lignin sulfonate, 1 part of carbon black and 4.2 parts of barium sulfate, and 1.7% of carbon nano tube based on the total mass of the anode expanding agent is added, wherein the length of the carbon nano tube is 1.0 mu m. The preparation method of the anode expanding agent comprises the following steps:
(1) Firstly, mixing carbon black, carbon nano tubes, barium sulfate and sodium lignin sulfonate in a mixer;
(2) Then transferring the mixture into a ball mill for ball milling for 30min to obtain the negative electrode expanding agent for the storage battery;
the specific mixing method in the mixer in the step (1) is as follows: firstly mixing carbon black, carbon nano tube and sodium lignin sulfonate for 9min, then adding barium sulfate for mixing for 15min.
Example 12:
the anode expanding agent for the storage battery comprises the following raw materials in parts by weight: 1 part of sodium lignin sulfonate, 1 part of carbon black and 4.2 parts of barium sulfate, and 1.8% of carbon nano tube based on the total mass of the anode expanding agent is added, wherein the length of the carbon nano tube is 1.0 mu m. The preparation method of the anode expanding agent comprises the following steps:
(1) Firstly, mixing carbon black, carbon nano tubes, barium sulfate and sodium lignin sulfonate in a mixer;
(2) Then transferring the mixture into a ball mill for ball milling for 30min to obtain the negative electrode expanding agent for the storage battery;
the specific mixing method in the mixer in the step (1) is as follows: firstly mixing carbon black, carbon nano tube and sodium lignin sulfonate for 9min, then adding barium sulfate for mixing for 15min.
Example 13:
the anode expanding agent for the storage battery comprises the following raw materials in parts by weight: 1 part of sodium lignin sulfonate, 1 part of carbon black and 4.2 parts of barium sulfate, and 1.9% of carbon nano tube based on the total mass of the anode expanding agent is added, wherein the length of the carbon nano tube is 1.0 mu m. The preparation method of the anode expanding agent comprises the following steps:
(1) Firstly, mixing carbon black, carbon nano tubes, barium sulfate and sodium lignin sulfonate in a mixer;
(2) Then transferring the mixture into a ball mill for ball milling for 30min to obtain the negative electrode expanding agent for the storage battery;
the specific mixing method in the mixer in the step (1) is as follows: firstly mixing carbon black, carbon nano tube and sodium lignin sulfonate for 9min, then adding barium sulfate for mixing for 15min.
Example 14:
the anode expanding agent for the storage battery comprises the following raw materials in parts by weight: 1 part of sodium lignin sulfonate, 1 part of carbon black and 4.2 parts of barium sulfate, and 2.0% of carbon nano tubes based on the total mass of the negative electrode expanding agent are added, wherein the length of the carbon nano tubes is 1.0 mu m. The preparation method of the anode expanding agent comprises the following steps:
(1) Firstly, mixing carbon black, carbon nano tubes, barium sulfate and sodium lignin sulfonate in a mixer;
(2) Then transferring the mixture into a ball mill for ball milling for 30min to obtain the negative electrode expanding agent for the storage battery;
the specific mixing method in the mixer in the step (1) is as follows: firstly mixing carbon black, carbon nano tube and sodium lignin sulfonate for 9min, then adding barium sulfate for mixing for 15min.
Example 15:
the anode expanding agent for the storage battery comprises the following raw materials in parts by weight: 1 part of sodium lignin sulfonate, 1 part of carbon black and 4.2 parts of barium sulfate, and 2.1% of carbon nano tubes based on the total mass of the negative electrode expanding agent are added, wherein the length of the carbon nano tubes is 1.0 mu m. The preparation method of the anode expanding agent comprises the following steps:
(1) Firstly, mixing carbon black, carbon nano tubes, barium sulfate and sodium lignin sulfonate in a mixer;
(2) Then transferring the mixture into a ball mill for ball milling for 30min to obtain the negative electrode expanding agent for the storage battery;
the specific mixing method in the mixer in the step (1) is as follows: firstly mixing carbon black, carbon nano tube and sodium lignin sulfonate for 9min, then adding barium sulfate for mixing for 15min.
By testing examples 5-15, in which we found that examples 5-14 had a number of cycles of 24-26 charge-discharge cycles and example 15 had a number of cycles of 23, we found that the cycle performance was significantly improved by the carbon nanotubes having a mass of 1% -2%, probably because the carbon nanotubes had a certain length, which increased the synergistic effect of barium sulfate and sodium lignin sulfonate, thereby improving the cycle performance as a whole.
It should be noted that in this document, relational terms such as "first" and "second" and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. The terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises an element.
The above embodiments are merely preferred embodiments of the present application, and the present application is not limited in any way, and any person skilled in the art may make some changes or modifications to the equivalent embodiments without departing from the scope of the present application, but any simple modification, equivalent changes and modifications to the above embodiments according to the technical principles of the present application are still within the scope of the present application.
Claims (10)
1. The negative electrode expanding agent for the storage battery is characterized by comprising sodium lignin sulfonate, carbon black, carbon nanotubes and barium sulfate, wherein the mass ratio of the sodium lignin sulfonate to the barium sulfate is 1:4-1:4.5.
2. The negative electrode swelling agent for a secondary battery according to claim 1, wherein the negative electrode swelling agent is produced by:
(1) Firstly, mixing carbon black, carbon nano tubes, barium sulfate and sodium lignin sulfonate in a mixer;
(2) Then transferring the mixture into a ball mill for ball milling for 30min to obtain the negative electrode expanding agent for the storage battery;
the specific mixing method in the mixer in the step (1) is as follows: firstly mixing carbon black, carbon nano tube and sodium lignin sulfonate for 9min, then adding barium sulfate for mixing for 15min.
3. The negative electrode swelling agent for a secondary battery according to claim 1, wherein the mass ratio of the sodium lignin sulfonate to the barium sulfate is 1:4.2 to 1:4.5 in terms of mass components.
4. The negative electrode swelling agent for a secondary battery according to claim 1, wherein the carbon nanotube has a length of 1.0 to 1.5 μm.
5. The anode expander for a secondary battery according to claim 1, wherein the mass of the carbon nanotubes is 1% to 2% based on the total mass of the anode expander.
6. The negative electrode swelling agent for a secondary battery according to claim 1, wherein the specific surface area of the carbon nanotube is 100m 2 /g-200m 2 /g。
7. The negative electrode swelling agent for a secondary battery according to claim 1, wherein the carbon nanotube has a tube diameter of 4nm to 4.5nm.
8. The negative electrode swelling agent for a secondary battery according to claim 1, wherein the carbon nanotubes are single-walled carbon nanotubes.
9. The negative electrode swelling agent for a secondary battery according to claim 1, wherein the carbon black has a particle diameter of 0.05 to 10 μm.
10. The negative electrode swelling agent for a secondary battery according to claim 1, wherein the carbon black has a particle diameter of 4 to 5 μm.
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| CN103337624A (en) * | 2013-06-28 | 2013-10-02 | 风帆股份有限公司 | Lead-acid storage battery negative lead plaster capable of inhibiting hydrogen evolution and preparation method |
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