CN107611442A - A kind of preparation method of low temperature resistant lead carbon battery lignin composite additives to negative electrodes - Google Patents
A kind of preparation method of low temperature resistant lead carbon battery lignin composite additives to negative electrodes Download PDFInfo
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- CN107611442A CN107611442A CN201710730729.8A CN201710730729A CN107611442A CN 107611442 A CN107611442 A CN 107611442A CN 201710730729 A CN201710730729 A CN 201710730729A CN 107611442 A CN107611442 A CN 107611442A
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- low temperature
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- negative electrodes
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The present invention relates to lead carbon battery field, specifically, it is related to a kind of preparation method of low temperature resistant lead carbon battery lignin composite additives to negative electrodes, after secondary sulfonation is carried out to sodium lignin sulfonate and improves sulfonation degree, sulfuric acid solution immersion predissolve is carried out, retains the lignin sulfonic acid sodium additives that relative molecular weight is higher, stability is good.Select wooden class activated carbon and sodium lignin sulfonate mixed and modified, sulfonic acid group is introduced on the activated carbon of rock-steady structure；And using activated carbon as absorption core, adsorb insoluble and immersion dissolving the sodium lignin sulfonate after secondary sulfonation, fix three kinds of sulfonic acid groups, modified lignin resin class cathode additive agent is made, sulfonic acid group is from GND dissolution during so as to reduce use, the utilization rate of sulfonic acid group is improved, reaches the purpose for extending battery cycle life and further improving cryogenic property.
Description
Technical field
The present invention relates to lead carbon battery field, in particular to a kind of low temperature resistant lead carbon battery lignin negative pole
The preparation method of compound additive.
Background technology
Lignosulphonates are applied to lead accumulator negative pole, and its most prominent contribution is exactly to be obviously improved negative pole at low temperature
High-rate discharge ability.When lignosulfonates add GND as additive, lignosulphonates closely adsorb
Active material surface, careful, porous crystalline texture is formed, by the specific surface area of active material from about 0.2m2/ g is brought up to
0.8m2/ g, negative electrode active material surface area shrinkage caused by sulfation crystallizes in charge and discharge cycles is prevented, negative pole is lived
Property the actual polarized current density that is subjected under conditions of discharge current is certain of material it is smaller, negative pole degree of polarization reduces, and has
Effect delays the rapid increase of negative pole current potential, improves the low temperature discharge ability of negative pole.
Lead carbon battery ties up in conventional lead storage cells negative electrode active material and introduces absorbent charcoal material, play its super capacitor with
Faraday's lead accumulator double grading, compared with common lead accumulator, charging rate can improve nearly 8 times during normal temperature use, electric discharge
Power improves nearly 3 times, simultaneously because the high-specific surface area of carbon material and negative pole swelling agent such as sodium lignin sulfonate etc. act on, makes to bear
Pole crystal grain further refines, and significantly lifts high magnification partial state of charge cycle life；Such as application publication number be 103259052A,
The Chinese invention patents such as 102983327A, 103855388A, be provided which it is a kind of improve battery cryogenic property lead carbon battery with carbon/
Carbon composite, compared to common lead accumulator low temperature（-15℃）2hr discharge capacities only have 50%, and lead carbon battery can reach 75~
85%, but capacitance loss is still very high, especially in more high current（Such as 1C, 3C）Capacity and cycle life loss during electric discharge
It is more serious.
Battery researcher is attempted to enter one by increasing the addition of swelling agent sodium lignin sulfonate and carbon material
Step improves the cryogenic property of lead carbon battery, but negative electrode active material volume excessively expands, so that between negative electrode active material
Adhesion declines, and electrode impedance increase, activation polarization aggravation, is unfavorable for the lifting of negative pole cryogenic property on the contrary.Also there is research
By improving the sulfonation degree of lignosulfonates, increase the dispersion efficiency of active material in its unit volume, can improve in early stage
The low temperature high-rate performance of lead carbon battery, but the raising of sulfonation degree can increase its solubility in sulfuric acid electrolyte, lignin
Sodium sulfonate is dissolved out from negative plate, causes the reduction of negative plate capacity, while the sodium lignin sulfonate dissolved easily passes through electricity
Migration or concentration difference diffusion migrate to positive electrode surface or nearby, and then positive pole be oxidized decompose, generation small-molecular-weight by-product
Thing, therefore cycle life can be influenceed on the contrary.
The content of the invention
It is of the invention in order to solve above-mentioned technological deficiency existing for lead carbon battery negative electrode active material additive prior art
Purpose is to provide a kind of preparation method of low temperature resistant lead carbon battery lignin composite additives to negative electrodes, further improves lead
The low temperature high current service behaviour of carbon battery.
It is including following according to the preparation method of the low temperature resistant lead carbon battery lignin composite additives to negative electrodes of the present invention
Step：
（1）Each 1 part of mixing of wooden class activated carbon and lead accumulator lignin sulfonic acid sodium additives is weighed, adds 10 parts of water stirrings
Uniformly, the pH value that solution is adjusted with dilute NaOH solution is 10~11, and mixed solution then is heated into 75 DEG C, instilled while stirring
1 part of formalin；
（2）Above-mentioned mixed liquor is transferred to hydrothermal reaction kettle after insulation reaction 2h, is 6~8 with dilute sulfuric acid regulation pH value, adds
0.5~1 part of sodium sulfite, hydro-thermal reaction 4h at a temperature of 140 DEG C are placed in after stirring；
（3）1.28g/cm is soaked in by above-mentioned reaction product cold filtration, then by solids3Sulfuric acid solution in, stand 24h after
30min is stirred, filtered, cleaning, dries acquisition modified lignin resin class cathode additive agent.
Preferably, it is that activated carbon is made in raw material that the wooden class activated carbon, which includes mao bamboon, sugarcane, reed, wheat straw, needle,
One or more.
In any of the above-described scheme preferably, the modified lignin resin class cathode additive agent is sulphur-modified wooden class
The mixture of activated carbon and insoluble secondary lignosulfonate sodium sulfonate.
In any of the above-described scheme preferably, the wooden class charcoal absorption of sulfonation modifying has the（3）It is molten in step
The secondary lignosulfonate sodium sulfonate of solution.
Present invention also offers a kind of low temperature resistant lead carbon battery, and its negative electrode active material is using addition lead powder quality 2-8 ‰
By the above method prepare low temperature resistant lead carbon battery lignin composite negative pole additive.
The low temperature resistant lead carbon battery of the present invention is with the preparation method of lignin composite additives to negative electrodes to sulfomethylated lignin
After sour sodium carries out secondary sulfonation raising sulfonation degree, sulfuric acid solution immersion predissolve is carried out, reservation molecular weight is of a relatively high, stability
Good lignin sulfonic acid sodium additives.Meanwhile by selecting wooden class activated carbon and sodium lignin sulfonate mixed and modified, stable
Sulfonate group is introduced on the activated carbon of structure；And using the activated carbon as absorption core, adsorb insoluble after secondary sulfonation and
The sodium lignin sulfonate of dissolving is soaked, makes three kinds of sulfonic acid groups（Activated carbon modified sulfonic acid group, soluble and insoluble secondary sulphur
Change lignosulphonic acid group）It is fixed, low temperature resistant lead carbon battery lignin composite additives to negative electrodes is made, so as to reduce lead charcoal electricity
Pond negative electrode active material additive sulfonic acid group improves the utilization rate of sulfonic acid group, reaches raising active material from negative pole dissolution
Utilization rate, extend battery cycle life and further improve the purpose of low temperature charge-discharge performance.
Brief description of the drawings
Fig. 1 be according to the present invention low temperature resistant lead carbon battery lignin composite additives to negative electrodes preparation method and adopt
With the low temperature resistant lead carbon battery low temperature capacity of the property-modifying additive（2hr）Test result.
Fig. 2 be according to the present invention low temperature resistant lead carbon battery lignin composite additives to negative electrodes preparation method and adopt
With the low temperature resistant lead carbon battery low temperature capacity of the property-modifying additive（1hr）Test result.
Embodiment
It is that the following description is substantially merely exemplary and be not intended to limit the disclosure, application or purposes.Below
It is specific with the preparation method of lignin composite additives to negative electrodes to the low temperature resistant lead carbon battery of the present invention with reference to Figure of description
Embodiment is further described.
A kind of preparation method of low temperature resistant lead carbon battery lignin composite additives to negative electrodes of the present invention, including it is following
Step：
（1）Each 1 part of mixing of wooden class activated carbon and lead accumulator lignin sulfonic acid sodium additives is weighed, adds 10 parts of water stirrings
Uniformly, the pH value that solution is adjusted with dilute NaOH solution is 10~11, and mixed solution then is heated into 75 DEG C, instilled while stirring
1 part of formalin；
（2）Above-mentioned mixed liquor is transferred to hydrothermal reaction kettle after insulation reaction 2h, is 6~8 with dilute sulfuric acid regulation pH value, adds
0.5~1 part of sodium sulfite, hydro-thermal reaction 4h at a temperature of 140 DEG C are placed in after stirring；
（3）1.28g/cm is soaked in by above-mentioned reaction product cold filtration, then by solids3Sulfuric acid solution in, stand 24h after
30min is stirred, filtered, cleaning, dries acquisition modified lignin resin class cathode additive agent.
In the present embodiment, the wooden class activated carbon is made including mao bamboon, sugarcane, reed, wheat straw, needle etc. for raw material
The one or more of activated carbon.
In the present embodiment, the modified lignin resin class cathode additive agent is sulphur-modified wooden class activated carbon and insoluble
The mixture of the secondary lignosulfonate sodium sulfonate of property.
In the present embodiment, the wooden class charcoal absorption of the sulfonation modifying has the secondary sulfonation wood dissolved in third step
Quality sodium sulfonate.
As shown in Figure 1, 2, using the low temperature resistant lead carbon battery lignin composite additives to negative electrodes according to the present invention
The lead carbon battery low temperature capacity test result for the property-modifying additive that preparation method obtains.
Comparative example 1：
1）Weigh 5g lead-acid battery anode additive sodium lignin sulfonates（Prolong side wood sodium）, add 50g water and stir, use is dilute
The pH value of NaOH solution regulation mixed liquor is 11, and mixed liquor then is heated into 75 DEG C, instills 5g formalins while stirring
（Mass fraction 37%）；Above-mentioned mixed liquor is transferred to hydrothermal reaction kettle after insulation reaction 2h, pH value is adjusted with dilute sulfuric acid aqueous solution
For 6-7,3g sodium sulfites are added, hydro-thermal reaction 4h at 140 DEG C is placed in after stirring；By above-mentioned reaction product cold filtration,
Cleaning, obtain modified sodium lignosulfonate A after drying；
2）A solids are taken, are soaked in 1.28g/cm3Aqueous sulfuric acid in, stand 24h after, it is filtered, cleaning, dry after obtain
Insoluble sodium lignin sulfonate B；
3）Sodium lignin sulfonate is determined using ion exchange-conductometry respectively（Prolong side wood sodium）And A, B sulfonation degree, through surveying
Try sodium lignin sulfonate（Prolong side wood sodium）Sulfonation degree is 0.62mmol/g, and A sulfonation degrees are 0.82mmol/g, and B sulfonation degrees are
0.66mmol/g。
Embodiment 1：
1）Weigh bamboo charcoal, lead-acid battery anode additive sodium lignin sulfonate（Prolong side wood sodium）Each 5g, it is equal to add the stirring of 50g water
Even, the pH value that mixed liquor is adjusted with dilute NaOH aqueous solution is 11, and mixed liquor then is heated into 75 DEG C, instills 5g first while stirring
The aldehyde aqueous solution（Mass fraction 37%）；Above-mentioned mixed liquor is transferred to hydrothermal reaction kettle after insulation reaction 2h, pH is adjusted with dilute sulfuric acid
It is worth for 6-7, adds 3g sodium sulfites, hydro-thermal reaction 4h at 140 DEG C is placed in after stirring；Above-mentioned reaction product is cooled
Filter, cleaning, obtain modified lignin resin class cathode additive agent C after drying.
2）Part C solids are taken, are soaked in 1.28g/cm3Aqueous sulfuric acid in, stand 24h after stir 30min, pass through
Filter, cleaning, dry acquisition lignin composite additives to negative electrodes D.
3）Bamboo charcoal, sodium lignin sulfonate are determined using ion exchange-conductometry respectively（Prolong side wood sodium）Mixture and
C, D sulfonation degrees, after tested bamboo charcoal, sodium lignin sulfonate（Prolong side wood sodium）Sulfonation degree be 0.13mmol/g, C sulfonation degrees are
0.78mmol/g, D sulfonation degree are 0.77mmol/g.
Present invention also offers a kind of low temperature resistant lead carbon battery, and its negative pole is using addition lead powder quality 2-8 ‰ by above-mentioned
Low temperature resistant lead carbon battery lignin composite additives to negative electrodes prepared by method.Being found by Fig. 1, Fig. 2 discharge curve should
The performance test results of battery are as follows：
YEC-8A lead carbon battery activated carbon, 5 ‰ lignin of the 1# lead carbon batteries negative pole using addition lead powder quality 1.5%
Sodium sulfonate（Prolong side wood sodium）, other formulas and technique are with reference to conventional lead carbon battery negative pole preparation technology.
2# lead carbon batteries negative pole is using YEC-8A lead carbon batteries activated carbon, 5 ‰ sheet for adding lead powder quality 1.5%
Invention lignin composite additives to negative electrodes, other formulas and technique are with reference to conventional lead carbon battery negative pole preparation technology.
Above-mentioned 1#, 2# negative pole is equipped with certain company's commodity positive plate, is assembled into 12V10Ah lead carbon batteries.
- 15 DEG C of capacity of 1#, 2# battery（2hr）Test is as shown in figure 1, as seen from the figure, during the low temperature discharge of 1#, 2# battery
Between be 100min, 112min respectively, common lead carbon battery 2hr low temperature capacities only have the 83.3% of rated capacity, using wood of the invention
The lead carbon battery of quality class composite additives to negative electrodes reaches the 93% of rated capacity.
- 15 DEG C of capacity of 1#, 2# battery（1hr）Test is as shown in Fig. 2 as seen from the figure, during the low temperature discharge of 1#, 2# battery
Between be 48min, 52min respectively, common lead carbon battery 1hr low temperature capacities only have the 80.2% of rated capacity, using the present invention it is wooden
The lead carbon battery of plain class composite additives to negative electrodes reaches the 86.6% of rated capacity.
It will be apparent to those skilled in the art that the low temperature resistant lead carbon battery lignin composite additives to negative electrodes of the present invention
Preparation method include this specification in each several part any combination.As space is limited and in order that specification is concise, do not have herein
These combinations are discussed in detail one by one, but after having seen this specification, any combination for each several part being made up of this specification is formed
The scope of the present invention it is self-evident.
Claims (5)
1. a kind of preparation method of the low temperature resistant lead carbon battery preparation method of lignin composite additives to negative electrodes, its feature exist
Comprise the steps in it：
（1）Each 1 part of mixing of wooden class activated carbon and lead accumulator lignin sulfonic acid sodium additives is weighed, adds 10 parts of water stirrings
Uniformly, the pH value that solution is adjusted with dilute NaOH solution is 10~11, and mixed solution then is heated into 75 DEG C, instilled while stirring
1 part of formalin；
（2）Above-mentioned mixed liquor is transferred to hydrothermal reaction kettle after insulation reaction 2h, is 6~8 with dilute sulfuric acid regulation pH value, adds
0.5~1 part of sodium sulfite, hydro-thermal reaction 4h at a temperature of 140 DEG C are placed in after stirring；
（3）1.28g/cm is soaked in by above-mentioned reaction product cold filtration, then by solids3Sulfuric acid solution in, stand 24h after
30min is stirred, filtered, cleaning, dries acquisition modified lignin resin class cathode additive agent.
2. the preparation of the low temperature resistant lead carbon battery preparation method of lignin composite additives to negative electrodes as claimed in claim 1
Method, it is characterised in that：It is that activated carbon is made in raw material that the wooden class activated carbon, which includes mao bamboon, sugarcane, reed, wheat straw, needle,
One or more.
3. the preparation of the low temperature resistant lead carbon battery preparation method of lignin composite additives to negative electrodes as claimed in claim 1
Method, it is characterised in that：The modified lignin resin class cathode additive agent is sulphur-modified wooden class activated carbon and insoluble
The mixture of secondary lignosulfonate sodium sulfonate.
4. the preparation of the low temperature resistant lead carbon battery preparation method of lignin composite additives to negative electrodes as claimed in claim 3
Method, it is characterised in that：The wooden class charcoal absorption of sulfonation modifying has（3）The secondary lignosulfonate dissolved in step
Sodium sulfonate.
5. a kind of low temperature resistant lead carbon battery, its negative electrode active material is using addition lead powder quality 2~8 ‰ such as Claims 1 to 4
Any one of method prepare low temperature resistant lead carbon battery lignin composite additives to negative electrodes.
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| CN201710730729.8A CN107611442A (en) | 2017-08-23 | 2017-08-23 | A kind of preparation method of low temperature resistant lead carbon battery lignin composite additives to negative electrodes |
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| CN201710730729.8A CN107611442A (en) | 2017-08-23 | 2017-08-23 | A kind of preparation method of low temperature resistant lead carbon battery lignin composite additives to negative electrodes |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111384424A (en) * | 2019-11-05 | 2020-07-07 | 郑州大学 | Lignin-based complex electrolyte for aqueous zinc-ion battery and aqueous zinc-ion battery based on same |
| CN113437255A (en) * | 2021-05-26 | 2021-09-24 | 浙江南都电源动力股份有限公司 | Low-temperature negative pole piece and preparation method thereof |
-
2017
- 2017-08-23 CN CN201710730729.8A patent/CN107611442A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111384424A (en) * | 2019-11-05 | 2020-07-07 | 郑州大学 | Lignin-based complex electrolyte for aqueous zinc-ion battery and aqueous zinc-ion battery based on same |
| CN113437255A (en) * | 2021-05-26 | 2021-09-24 | 浙江南都电源动力股份有限公司 | Low-temperature negative pole piece and preparation method thereof |
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