CN108777289A - A kind of preprocess method of stable water-retaining type lead carbon battery negative material - Google Patents
A kind of preprocess method of stable water-retaining type lead carbon battery negative material Download PDFInfo
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- H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
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Abstract
The invention discloses a kind of preprocess methods of stable water-retaining type lead carbon battery negative material.The preprocess method of the negative material mainly comprises the following steps：A, activated carbon is added in lead nitrate solution and is ultrasonically treated, obtain stable suspension；B, hydrogen peroxide and ammonium hydroxide are slowly added dropwise into suspension, lead/carbon material is made in heating reaction；C, lead/carbon material is mixed with lead plaster, cathode additive agent, you can obtain the lead carbon battery negative material with good water-retaining property.The method has the advantages that：The present invention passes through supersound process, netted carbon structure is formed after so that carbon-based material is mixed with lead, the grain size of the lead sulfate formed in control discharge process, the lead sulfate to be formed is set fully to be restored in charging, carbon material is modified by hydrogen peroxide and ammonium hydroxide simultaneously, the hydrophilic functional group of material surface is made to increase, hydrophily enhancing, promote the hydroxyl ion being electrolysed to combine, significantly improves the water retention property of lead carbon battery.
Description
Technical field
The present invention relates to lead carbon battery fields, and in particular to the pretreatment of negative material, more particularly, to a kind of stable guarantor
The preprocess method of water type lead carbon battery negative material.
Background technology
Energy-storage battery technology is to restrict one of the key technology of intelligent grid energy storage industry development.Photovoltaic energy storage, wind-powered electricity generation storage
The energy storage fields such as energy and power grid frequency modulation peak regulation, it is desirable that battery has power density big, has extended cycle life the features such as relatively low with price.
The positive electrode active materials of wherein conventional lead acid battery are lead oxide, and negative electrode active material is lead.In order to improve traditional lead acid batteries
Cycle life is short, the shortcomings of charge-discharge electric power is small, the charcoal with electric double layer capacitance characteristic is added in the cathode of lead-acid battery, will
Together with lead-acid battery and the blend of predominance of ultracapacitor, the advantages of both having played ultracapacitor large capacity charge and discharge,
The ratio energy advantage for having played lead-acid battery, here it is a kind of charcoals risen to enhance lead-acid battery, as lead carbon battery.
Currently, Lead-acid Battery Technology technique is very ripe, have that capacity is big, safety is good, at low cost, recyclable
The features such as, future will be the mainstream technology of weak mixed technology, but traditional lead acid batteries high current charge-discharge short life the problems such as system
The novel battery technology of the about popularization of the technology, lead carbon battery can solve this deficiency.Lead carbon battery by Carbon Materials with tradition
Negative material lead is mixed to form composite negative pole, after cathode introduces Carbon Materials, the sulfation phenomenon that can be effectively improved under PSoC,
Charge acceptance and high rate performance are improved, so that battery is had the characteristics that high power discharge, quick charge and discharge, long circulation life, is
One of current relatively practicable energy storage technology route.
Number of patent application 201610718669.3 discloses a kind of preparation side of lead carbon battery lead-graphene composite material
Method prepares lead-graphene composite material using the methods of simple liquid phase reactor, centrifugation, high temperature sintering, simple for process, production
It is efficient, it is advantageously implemented large-scale production, it is easy to utilize.Lead-graphene composite material of gained has high analysis
Hydrogen overpotential solves the problems, such as that graphene overpotential of hydrogen evolution is low, improves the capacitive property of graphene well.The composite wood
The high rate performance, charge acceptance and HRPSOC that material can effectively improve battery as the additive of lead carbon battery cathode follow
The ring service life reduces the water loss of lead carbon battery, has a extensive future.
Number of patent application 201610839022.6 discloses a kind of preparation method and its cathode of lead carbon battery composite negative pole
And application.First by porous carbon in-situ preparation lead sulfate method improve carbon material bulk density, reduce carbon material with
Then the density contrast of lead powder is uniformly mixed modified activated carbon with lead powder, additive using shearing method realization, to prepare height
The lead carbon battery composite negative pole of performance.Lead carbon battery composite negative pole prepared by method involved by the invention has than conventional lead acid electricity
Pond high charge and discharge invertibity, charge and discharge circulation life and charge acceptance, it is easy to accomplish the characteristics of large-scale production.
Number of patent application 201510466243.9 discloses a kind of preparation method of lead carbon battery cathode.Including with cream, solid
Change dry and chemical conversion, is made of alloy grid and active material.The invention is novel more by being added into cathode lead plaster
Hole carbon material, prepares a kind of NEW Pb carbon battery cathode, and the addition of the carbon material can change negative electrode active material chemical conversion
Pattern, structure and reactive mode afterwards.The lead carbon battery assembled with the cathode of the invention can be under high rate partial state of charge
Good cycle performance is shown, delays the irreversible sulfation process of battery cathode when high current works significantly, to
Its service life is significantly improved, has huge foreground in wind light generation and power grid energy storage and new-energy automobile power battery application aspect,
And the invention simple process and low cost is honest and clean, is easy to industrialization.
Number of patent application 201710880361.3 discloses a kind of lead carbon battery graphene oxide/active-carbon fibre material
Complex method, its step are as follows：Set component is pressed first measures broken biomass fiber, graphene oxide and NaOH；25 ~ 40
Under DEG C environment temperature, the broken biomass fiber of measurement is added in the mixed solution being made of graphene oxide and NaOH, so
Make homogeneous mixing using ultrasonic wave afterwards, then shakes up processing.Mixture after homogenization is sent into vacuum drying chamber and is made
Low temperature drying is handled, and finally obtains graphene oxide/Active carbon fiber composite material.The material is applied to pole plate manufacture, can
Slow down 1 ~ 2 times of lead carbon battery capacity attenuation speed, promotes 1 times of mating battery cycle life or more.
It can be seen that lead carbon battery has the Carbon Materials release of capacitance characteristic or receives electric current in the prior art, to press down
The sulfation of cathode processed, the novel battery to prolong the service life；Since the density contrast of lead and carbon is away from larger, in charge and discharge process
Middle cathode is easily by oxidation liberation of hydrogen, the problems such as causing battery dehydration serious, influence battery life.
Invention content
Effectively to solve above-mentioned technical problem, the present invention proposes a kind of the pre- of stable water-retaining type lead carbon battery negative material
Processing method can effectively improve the water retention property of lead carbon battery, to promote battery life.
The specific technical solution of the present invention is as follows：
A kind of preprocess method of stable water-retaining type lead carbon battery negative material, the preprocess method by by activated carbon in nitre
It is ultrasonically treated in lead plumbate solution, then is reacted with hydrogen peroxide and ammonium hydroxide, lead/carbon material obtained and lead plaster, cathode additive agent
It mixes and realizes, specific implementation steps are：
A, activated carbon is added in the lead nitrate solution that mass concentration is 40 ~ 50%, is ultrasonically treated, activated carbon is made to form reticulated carbon
Structure obtains stable suspension；
B, the hydrogen peroxide that mass concentration is 35% and the ammonium hydroxide that mass concentration is 25% are slowly added dropwise into the suspension of step a, adds
Heat is reacted, and after reaction, is filtered, washed, is dried, and lead/carbon material is made；
C, lead/carbon material made from step b is mixed with lead plaster, cathode additive agent, you can obtain the lead with good water-retaining property
Carbon battery negative material.
Preferably, in the step a, 25 ~ 40 parts by weight of activated carbon, 60 ~ 75 parts by weight of lead nitrate solution.
Preferably, in the step a, the supersonic frequency of supersound process is 30 ~ 50kHz, and spacing is 5 ~ 10cm, processing time
For 15 ~ 30min.
Preferably, in the step b, 50 ~ 65 parts by weight of suspension, 10 ~ 15 parts by weight of hydrogen peroxide, 25 ~ 35 weight of ammonium hydroxide
Part.
Preferably, in the step b, the rate of addition of hydrogen peroxide is 1.2 ~ 1.5mL/min, and the rate of addition of ammonium hydroxide is
1.5~2mL/min。
Preferably, in the step b, reaction temperature is 50 ~ 60 DEG C, and the time is 100 ~ 130min.
Preferably, in the step c, the group of lead plaster becomes 12 ~ 15 parts by weight of brown lead oxide, 10 ~ 15 weight of basic lead sulphate
Measure part, 2 ~ 4 parts by weight of metallic lead, 3 ~ 5 parts by weight of lead hydroxide, 61 ~ 73 parts by weight of water.
Preferably, in the step c, cathode additive agent is in sodium lignosulfonate, barium sulfate, carbon black, aerosil
At least one.
Preferably, in the step c, 82 ~ 89 parts by weight of lead/carbon material, 10 ~ 15 parts by weight of lead plaster, cathode additive agent 1 ~ 3
Parts by weight.
Carbon-based material is uniformly mixed with lead, forms netted carbon structure, is applied on the surface of porous Reticulated vitreous carbon a thin layer of
Pure lead as modification just formed lead plating reticulated carbon.The netted carbon electrode of lead plating can nearly all show electricity identical with simple metal lead
Chemical property so that positive corrosion resistance significantly improves, and then controls the reaction process in lead sulfate generating process.Using hydrogen peroxide
Carbon material surface is modified with ammonium hydroxide oxidation processes, carbon-based material surface chemical property can be made to change, surface acidity
Oxygen-containing group increases so that its surface isoelectric point reduces, and improves hydrophily, and then improves chemical property.
The above of the present invention proposes a kind of preprocess method of stable water-retaining type lead carbon battery negative material, passes through ultrasound
Processing makes carbon-based material uniformly be mixed with lead, forms netted carbon structure, controls the grain size of the lead sulfate formed in discharge process, keeps away
The formation for exempting from bulky grain lead sulfate enables the lead sulfate to be formed fully to be restored in charging.Simultaneously because hydrogen peroxide and ammonium hydroxide
Carbon material is modified, the hydrophilics such as carboxyl, amino, hydroxyl of material surface functional group is made to increase, promotes the hydrogen being electrolysed
Oxonium ion combines.
Beneficial effects of the present invention are：
Stablize water-retaining type lead carbon battery negative material 1. proposing and being modified to carbon material using hydrogen peroxide and ammonium hydroxide
Preprocess method.
2. the present invention forms netted carbon structure, controls discharge process by being ultrasonically treated after so that carbon-based material is mixed with lead
The grain size of the lead sulfate of middle formation avoids the formation of bulky grain lead sulfate, and the lead sulfate to be formed is enable fully to be gone back in charging
It is former.
3. the present invention is modified carbon material by hydrogen peroxide and ammonium hydroxide, the hydrophilic functional group of material surface is made to increase
Add, hydrophily enhancing promotes the hydroxyl ion being electrolysed to combine, significantly improves the water retention property of lead carbon battery.
Specific implementation mode
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
A, activated carbon is added in the lead nitrate solution that mass concentration is 45%, is ultrasonically treated, activated carbon is made to form reticulated carbon knot
Structure obtains stable suspension；
B, the hydrogen peroxide that mass concentration is 35% and the ammonium hydroxide that mass concentration is 25% are slowly added dropwise into the suspension of step a, adds
Heat is reacted, and after reaction, is filtered, washed, is dried, and lead/carbon material is made；
C, lead/carbon material made from step b is mixed with lead plaster, cathode additive agent, you can obtain the lead with good water-retaining property
Carbon battery negative material.
In step c, cathode additive agent is sodium lignosulfonate.
In step a, 32 parts by weight of activated carbon, 68 parts by weight of lead nitrate solution；In step b, 57 parts by weight of suspension, dioxygen
13 parts by weight of water, 30 parts by weight of ammonium hydroxide；In step c, the group of lead plaster becomes 14 parts by weight of brown lead oxide, 14 weight of basic lead sulphate
Part, 3 parts by weight of metallic lead, 4 parts by weight of lead hydroxide, 65 parts by weight of water；In step c, 85 parts by weight of lead/carbon material, lead plaster 13
Parts by weight, 2 parts by weight of cathode additive agent.
In step a, the supersonic frequency of supersound process is 40kHz, spacing 8cm, processing time 25min；In step b,
The rate of addition of hydrogen peroxide is 1.4mL/min, and the rate of addition of ammonium hydroxide is 1.8mL/min；In step b, reaction temperature is 55 DEG C,
Time is 115min.
Embodiment 2
A, activated carbon is added in the lead nitrate solution that mass concentration is 40%, is ultrasonically treated, activated carbon is made to form reticulated carbon knot
Structure obtains stable suspension；
B, the hydrogen peroxide that mass concentration is 35% and the ammonium hydroxide that mass concentration is 25% are slowly added dropwise into the suspension of step a, adds
Heat is reacted, and after reaction, is filtered, washed, is dried, and lead/carbon material is made；
C, lead/carbon material made from step b is mixed with lead plaster, cathode additive agent, you can obtain the lead with good water-retaining property
Carbon battery negative material.
In step c, cathode additive agent is barium sulfate.
In step a, 25 parts by weight of activated carbon, 75 parts by weight of lead nitrate solution；In step b, 65 parts by weight of suspension, dioxygen
10 parts by weight of water, 25 parts by weight of ammonium hydroxide；In step c, the group of lead plaster becomes 12 parts by weight of brown lead oxide, 10 weight of basic lead sulphate
Part, 2 parts by weight of metallic lead, 3 parts by weight of lead hydroxide, 73 parts by weight of water；In step c, 89 parts by weight of lead/carbon material, lead plaster 10
Parts by weight, 1 parts by weight of cathode additive agent.
In step a, the supersonic frequency of supersound process is 30kHz, spacing 5m, processing time 30min；It is double in step b
The rate of addition of oxygen water is 1.2mL/min, and the rate of addition of ammonium hydroxide is 1.5mL/min；In step b, reaction temperature is 50 DEG C, when
Between be 130min.
Embodiment 3
A, activated carbon is added in the lead nitrate solution that mass concentration is 50%, is ultrasonically treated, activated carbon is made to form reticulated carbon knot
Structure obtains stable suspension；
B, the hydrogen peroxide that mass concentration is 35% and the ammonium hydroxide that mass concentration is 25% are slowly added dropwise into the suspension of step a, adds
Heat is reacted, and after reaction, is filtered, washed, is dried, and lead/carbon material is made；
C, lead/carbon material made from step b is mixed with lead plaster, cathode additive agent, you can obtain the lead with good water-retaining property
Carbon battery negative material.
In step c, cathode additive agent is carbon black.
In step a, 40 parts by weight of activated carbon, 60 parts by weight of lead nitrate solution；In step b, 50 parts by weight of suspension, dioxygen
15 parts by weight of water, 35 parts by weight of ammonium hydroxide；In step c, the group of lead plaster becomes 15 parts by weight of brown lead oxide, 15 weight of basic lead sulphate
Part, 4 parts by weight of metallic lead, 5 parts by weight of lead hydroxide, 61 parts by weight of water；In step c, 82 parts by weight of lead/carbon material, lead plaster 15
Parts by weight, 3 parts by weight of cathode additive agent.
In step a, the supersonic frequency of supersound process is 50kHz, spacing 10cm, processing time 15min；In step b,
The rate of addition of hydrogen peroxide is 1.5mL/min, and the rate of addition of ammonium hydroxide is 2mL/min；In step b, reaction temperature is 60 DEG C, when
Between be 100min.
Embodiment 4
A, activated carbon is added in the lead nitrate solution that mass concentration is 42%, is ultrasonically treated, activated carbon is made to form reticulated carbon knot
Structure obtains stable suspension；
B, the hydrogen peroxide that mass concentration is 35% and the ammonium hydroxide that mass concentration is 25% are slowly added dropwise into the suspension of step a, adds
Heat is reacted, and after reaction, is filtered, washed, is dried, and lead/carbon material is made；
C, lead/carbon material made from step b is mixed with lead plaster, cathode additive agent, you can obtain the lead with good water-retaining property
Carbon battery negative material.
In step c, cathode additive agent is carbon black.
In step a, 30 parts by weight of activated carbon, 70 parts by weight of lead nitrate solution；In step b, 60 parts by weight of suspension, dioxygen
12 parts by weight of water, 28 parts by weight of ammonium hydroxide；In step c, the group of lead plaster becomes 13 parts by weight of brown lead oxide, 12 weight of basic lead sulphate
Part, 2 parts by weight of metallic lead, 3 parts by weight of lead hydroxide, 70 parts by weight of water；In step c, 87 parts by weight of lead/carbon material, lead plaster 12
Parts by weight, 1 parts by weight of cathode additive agent.
In step a, the supersonic frequency of supersound process is 35kHz, spacing 8cm, processing time 25min；In step b,
The rate of addition of hydrogen peroxide is 1.3mL/min, and the rate of addition of ammonium hydroxide is 1.6mL/min；In step b, reaction temperature is 52 DEG C,
Time is 120min.
Embodiment 5
A, activated carbon is added in the lead nitrate solution that mass concentration is 47%, is ultrasonically treated, activated carbon is made to form reticulated carbon knot
Structure obtains stable suspension；
B, the hydrogen peroxide that mass concentration is 35% and the ammonium hydroxide that mass concentration is 25% are slowly added dropwise into the suspension of step a, adds
Heat is reacted, and after reaction, is filtered, washed, is dried, and lead/carbon material is made；
C, lead/carbon material made from step b is mixed with lead plaster, cathode additive agent, you can obtain the lead with good water-retaining property
Carbon battery negative material.
In step c, cathode additive agent is sodium lignosulfonate.
In step a, 35 parts by weight of activated carbon, 63 parts by weight of lead nitrate solution；In step b, 54 parts by weight of suspension, dioxygen
14 parts by weight of water, 32 parts by weight of ammonium hydroxide；In step c, the group of lead plaster becomes 14 parts by weight of brown lead oxide, 13 weight of basic lead sulphate
Part, 3 parts by weight of metallic lead, 3 parts by weight of lead hydroxide, 68 parts by weight of water；In step c, 84 parts by weight of lead/carbon material, lead plaster 14
Parts by weight, 2 parts by weight of cathode additive agent.
In step a, the supersonic frequency of supersound process is 45kHz, spacing 8cm, processing time 20min；In step b,
The rate of addition of hydrogen peroxide is 1.4mL/min, and the rate of addition of ammonium hydroxide is 1.8mL/min；In step b, reaction temperature is 58 DEG C,
Time is 120min.
Comparative example 1
A, activated carbon is added in the lead nitrate solution that mass concentration is 47%, is ultrasonically treated, activated carbon is made to form reticulated carbon knot
Structure obtains stable suspension；
B, it is reacted to the heating of the suspension of step a, after reaction, is filtered, washed, dries, lead/carbon material is made；
C, lead/carbon material made from step b is mixed with lead plaster, cathode additive agent, you can obtain the lead with good water-retaining property
Carbon battery negative material.
In step c, cathode additive agent is sodium lignosulfonate.
In step a, 35 parts by weight of activated carbon, 63 parts by weight of lead nitrate solution；In step b, 54 parts by weight of suspension；Step
In c, the group of lead plaster becomes 14 parts by weight of brown lead oxide, 13 parts by weight of basic lead sulphate, 3 parts by weight of metallic lead, 3 weight of lead hydroxide
Measure part, 68 parts by weight of water；In step c, 84 parts by weight of lead/carbon material, 14 parts by weight of lead plaster, 2 parts by weight of cathode additive agent.
In step a, the supersonic frequency of supersound process is 45kHz, spacing 8cm, processing time 20min；In step b,
Reaction temperature is 58 DEG C, time 120min.
The lead carbon battery of the method for above-described embodiment 1 ~ 5 and comparative example 1 processing, tests its charge and discharge fluid loss, tests table
The method or condition of sign are as follows：
Percentage of water loss：The new battery lead carbon battery of 12V, 12Ah is made in the pretreated negative material of the present invention, is 25 DEG C, phase in temperature
The case where being 55%, 15V constant pressures to humidity, carries out charge and discharge fluid loss experiment, and the amount conversion dehydration of gas is generated according to side reaction
Amount, according to reduction formulas such as Avgadro constant and temperature, lose 18 grams of water will in the case where generating 25 DEG C about 36L gases
（Standard pressure）, and then calculate dilute tolerance using drainage, you can obtain fluid loss, measure respectively 12h, for 24 hours with mistake when 48h
Water.
The results are shown in Table 1.
Table 1：
Claims (9)
1. a kind of preprocess method of stable water-retaining type lead carbon battery negative material, it is characterised in that：The preprocess method is logical
It crosses and is ultrasonically treated activated carbon in lead nitrate solution, then reacted with hydrogen peroxide and ammonium hydroxide, lead/carbon material and lead obtained
Cream, cathode additive agent are mixed and are realized, specific implementation steps are：
A, activated carbon is added in the lead nitrate solution that mass concentration is 40 ~ 50%, is ultrasonically treated, activated carbon is made to form reticulated carbon
Structure obtains stable suspension；
B, the hydrogen peroxide that mass concentration is 35% and the ammonium hydroxide that mass concentration is 25% are slowly added dropwise into the suspension of step a, adds
Heat is reacted, and after reaction, is filtered, washed, is dried, and lead/carbon material is made；
C, lead/carbon material made from step b is mixed with lead plaster, cathode additive agent, you can obtain the lead with good water-retaining property
Carbon battery negative material.
2. a kind of preprocess method of stable water-retaining type lead carbon battery negative material according to claim 1, it is characterised in that：
In the step a, 25 ~ 40 parts by weight of activated carbon, 60 ~ 75 parts by weight of lead nitrate solution.
3. a kind of preprocess method of stable water-retaining type lead carbon battery negative material according to claim 1, it is characterised in that：
In the step a, the supersonic frequency of supersound process is 30 ~ 50kHz, and spacing is 5 ~ 10cm, and processing time is 15 ~ 30min.
4. a kind of preprocess method of stable water-retaining type lead carbon battery negative material according to claim 1, it is characterised in that：
In the step b, 50 ~ 65 parts by weight of suspension, 10 ~ 15 parts by weight of hydrogen peroxide, 25 ~ 35 parts by weight of ammonium hydroxide.
5. a kind of preprocess method of stable water-retaining type lead carbon battery negative material according to claim 1, it is characterised in that：
In the step b, the rate of addition of hydrogen peroxide is 1.2 ~ 1.5mL/min, and the rate of addition of ammonium hydroxide is 1.5 ~ 2mL/min.
6. a kind of preprocess method of stable water-retaining type lead carbon battery negative material according to claim 1, it is characterised in that：
In the step b, reaction temperature is 50 ~ 60 DEG C, and the time is 100 ~ 130min.
7. a kind of preprocess method of stable water-retaining type lead carbon battery negative material according to claim 1, it is characterised in that：
In the step c, the group of lead plaster becomes 12 ~ 15 parts by weight of brown lead oxide, 10 ~ 15 parts by weight of basic lead sulphate, 2 ~ 4 weight of metallic lead
Measure part, 3 ~ 5 parts by weight of lead hydroxide, 61 ~ 73 parts by weight of water.
8. a kind of preprocess method of stable water-retaining type lead carbon battery negative material according to claim 1, it is characterised in that：
In the step c, cathode additive agent is at least one of sodium lignosulfonate, barium sulfate, carbon black, aerosil.
9. a kind of preprocess method of stable water-retaining type lead carbon battery negative material according to claim 1, it is characterised in that：
In the step c, 82 ~ 89 parts by weight of lead/carbon material, 10 ~ 15 parts by weight of lead plaster, 1 ~ 3 parts by weight of cathode additive agent.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021091325A1 (en) * | 2019-11-08 | 2021-05-14 | 전남대학교산학협력단 | Negative electrode active material for lead storage battery and pb/c battery, preparation method therefor, and lead storage battery and pb/c battery comprising negative electrode active material |
| CN113224300A (en) * | 2021-04-15 | 2021-08-06 | 淄博火炬能源有限责任公司 | Preparation method of lead powder for negative electrode of lead-carbon battery |
-
2018
- 2018-05-04 CN CN201810418696.8A patent/CN108777289A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021091325A1 (en) * | 2019-11-08 | 2021-05-14 | 전남대학교산학협력단 | Negative electrode active material for lead storage battery and pb/c battery, preparation method therefor, and lead storage battery and pb/c battery comprising negative electrode active material |
| CN113224300A (en) * | 2021-04-15 | 2021-08-06 | 淄博火炬能源有限责任公司 | Preparation method of lead powder for negative electrode of lead-carbon battery |
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Application publication date: 20181109 |