CN108598387A - A kind of preparation method of lead-acid accumulator rare earth red lead - Google Patents

A kind of preparation method of lead-acid accumulator rare earth red lead Download PDF

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CN108598387A
CN108598387A CN201810235053.XA CN201810235053A CN108598387A CN 108598387 A CN108598387 A CN 108598387A CN 201810235053 A CN201810235053 A CN 201810235053A CN 108598387 A CN108598387 A CN 108598387A
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lead
rare earth
earth element
powder
preparation
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顾正玄
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
    • 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

Abstract

A kind of lead-acid accumulator preparation method of rare earth red lead, steps are as follows：S1. raw material lead is cut into lead, every block of bulk lead nearly weighs 4.5 kilograms, is placed in lead powder machine cylinder, prepares lead powder；S2. the lead powder in lead-power machine is taken out, is sent into mixing plant, then rare earth element is added in mixing plant；S3. the lead oxide powder containing rare earth element of preparation is introduced into bag filter；S4. it will be sent into Granulation Equipments containing rare earth element lead oxide powder in deduster, is granulated；S5. the lead oxide powder particle containing rare earth element of preparation is screened；S6. the lead oxide powder containing rare earth element that will be screened out, which is put into red lead calcined oxide stove, carries out calcined oxide；S7. by rare earth red lead made from calcined oxide, it is sampled chemical examination；S8. it examines qualified product to be packed using Tie Tong or container bag, can also want to pack according to client, storage is for sale.

Description

A kind of preparation method of lead-acid accumulator rare earth red lead
Technical field
The present invention relates to red lead production facility fields, and in particular to a kind of preparation side of lead-acid accumulator rare earth red lead Method.
Background technology
Red lead product is mainly used in the fields such as lead-acid accumulator, medicine, paint pigment, electronics at present, but red lead produces 98% use above of product in lead-acid accumulator, red lead product deleted as battery positive plate in lead-acid accumulator in active matter Matter, under normal circumstances, red lead with provide following reaction equation in cream and be changed into：
β-PbO2：Pb304+H2SO4→ β-Pb02+2PbSO4+2H2O
PbO2And Pb304Relationship by following formula state (wt%)：Pb304%=2.8662 × PbO2%
It is applied in lead-acid accumulator using the characteristics of red lead high oxidation amount, having improves solidification, shorten the chemical conversion time, carry High deep-circulating performance improves the functions such as battery capacity and service life：
1. easily controllable solidification
Solidification is the key that one of battery pole plates quality.Plate buckling, shedding, service life are all related with solidification.Produce defect Immediate cause be remaining free lead in lead powder (cream) quantity it is more.So cured main purpose is remaining lead in lead plaster (free lead) is reduced to 5% minimum below.
Solidification temperature is related with green plate quality, and the green plate newly painted contains metallic lead, exothermic oxidation when solidification, so Even if curing room temperature control at 40~60 DEG C, this will be far above inside pole plate.Thus real solidification temperature is difficult to grasp. The remaining free lead of red lead is less than 2%, with red lead cream, is whether applied alone (i.e. with the red lead of content 25%) or mixes, and trip It is eliminated from the relevant extra heat of lead, therefore is easier to grasp solidification.And due to that need not consider to aoxidize, three for controlling temperature and then generating Alkali formula and rare earth red lead (crystalline size and shape) are easily managed, and total hardening time can shorten, the effect for reaching saving, rising matter Fruit.
2. formation efficiency is higher
PbO in red lead2Account for about Pb3041/3, when positive plate is melted into will become subsequently generate PbO2Nucleus, make whole A active matter effectively changes, therefore can promote chemical conversion, and the chemical conversion time is made to shorten, and chemical conversion power consumption reduces, and so-called " flower piece " waste product Rate also declines.Tubular positive plate chemical conversion is more difficult, is often filled with the electricity of 10 times of capacity, and centre is subject to electric discharge 1~2 time, difficult Make the PbO of finished product2More than 80%, 25% red lead is added such as in lead powder, then is easy to make PbO in finished product2More than 80%；Apply cream Formula pole plate, if be melted into using battery case, especially with AGM, electrolyte flow is restricted, and is suitable for lead plaster to add red lead with profit especially Chemical conversion.Therefore the use of red lead can save the time in formation process and improve pole plate electric energy technique.
3. accumulator initial capacity is higher
Battery (positive plate) discharge capacity is derived from PbO2, PbO2There are mainly two types of crystal forms, and one is α-PbO2, one is cried β-PbO2.Their chemical composition is identical, mainly there is 2 points of differences：1. the crystallization of β types is tiny, size is approximately equal to the crystallization of α types Half, therefore real table area of the β types crystallization with bigger；2. β types are tetragonal, α types are orthorhombic forms, β types and electric discharge Product PbSO4Lattice parameter difference it is larger, PbSO4It cannot be along β-PbO2Lattice growth, and try hard to be formed the crystal grain of oneself, Since crystal lacks, coarse PbSO is then formed4Crystallization, has between coarse grain compared with big gap, H2S04It readily penetrates through PbSO4Layer, reaches active matter depths, pole plate depths active matter is enable to continue to discharge, so activity is higher, utilization rate is big, can give Go out more capacitance.To the PhO2 of identical quantity, discharge under identical current density, the capacitance that β types provide be more than α types to 1.5~3 times of the capacitance gone out.
After anode diachylon uses red lead, it is melted into the β-PbO of generation2It is more, so its use can improve initial capacity, Especially to fixed and industrial battery, international advanced lead-acid battery alliance (ALABC) has had proven to red lead for 2001 to VRIA electricity Tankage generates advantageous effect.
4. improving the cycle life of fixed battery
Present red lead production technology can be adjusted suitably to keep PbO in red lead2Content is higher, there is higher β-in lead powder PbO2Content can generate a large amount of rare earth red lead crystal, be conducive to the raising of battery cycle life after hardening.
It is described above function and significance of the red lead product in lead-acid accumulator.The service life of lead-acid accumulator at present It it is exactly the time in 1 year and a half or so, with the development of electric vehicle, New-energy electric vehicle, the market capacity of lead-acid accumulator is got over Come bigger, requirement of the people to the cruising ability of accumulator is higher and higher.In this way to the demand of the application study of novel storage battery It is more and more urgent.How the cruising ability of accumulator is improved, it is important to how to improve the charge storage ability of accumulator.If using dilute Reddle pellet product upgrades to red lead product, this target may be implemented.Because rare earth element is all very active gold Belong to element, the rare earth red lead of preparation is easily formed stable rare earth red lead crystal seed applied to accumulator, and then improves lead acid storage battery The capacitance in pond.
Invention content
Technical problem to be solved by the invention is to provide a kind of technical process is controllable, the high lead-acid accumulator of product quality With the preparation method of rare earth red lead.
A kind of lead-acid accumulator preparation method of rare earth red lead, steps are as follows：
S1. raw material lead is cut into lead, every block of bulk lead nearly weighs 4.5 kilograms, is placed in Shimadzu formula lead powder machine cylinder, allows Bulk lead constantly scrapes inner wall of rotary drum, avoids thin lead powder and is adhered on inner wall of rotary drum, to increase shot and inner wall of rotary drum Collision opportunity, increase lead powder yield, keep the oxidizability of lead powder consistent；
S2. the lead powder in Shimadzu formula lead-power machine is taken out, is sent into mixing plant, then rare earth member is added in mixing plant The weight ratio of element, lead powder and rare earth element is 100:1.8, it is stirred, is made containing rare earth member with 130 revs/min of rate The lead oxide powder of element；
S3. cool down dedusting：By the lead oxide powder containing rare earth element of preparation by air-introduced machine through conveyance conduit, in a steady stream not Disconnected is introduced into bag filter, removes lead dust, evades the generation of occupational hazards；
S4. it is granulated：It will be sent into Granulation Equipments containing rare earth element lead oxide powder in deduster, temperature is heated up to 100 DEG C Left and right, is granulated, and the graininess of 200 mesh or so is prepared；
S5. screening separation：The lead oxide powder particle containing rare earth element of preparation is screened, of 200 mesh or so Grain is separated into next process, and the remaining undesirable granulating working procedure that returns to is granulated again；
S6. calcined oxide：The lead oxide powder containing rare earth element come will be screened out to put into red lead calcined oxide stove, Calcined oxide is carried out at a high temperature of 600 degrees centigrade, it is both rare earth red lead product to aoxidize product obtained；
S7. product inspection：By rare earth red lead made from calcined oxide, it is sampled chemical examination, red lead product should be met National sector standard【HG/T4503-2013】, the content of rare earth met again in product is greater than or equal to 1.5%, otherwise for not Qualified products；
S8. finished product packing：Examine qualified product to be packed using Tie Tong or container bag, can also be wanted to need according to client into Row packaging, storage are for sale.
The rare earth element is lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), group more than one kind or two kinds of terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) and lutetium (Lu) It closes.
Mixing plant in the S2 steps is negative pressure mixing plant, and whipping step is divided into 3 stages completions：
1st stage：Negative pressure mixing plant sets negative pressure as 125mbar, and the addition of rare earth element is the 1/3 of total amount, temperature Degree is 50 DEG C, incorporation time 50 seconds；
2nd stage：Negative pressure mixing plant sets negative pressure as 105mbar, and the addition of rare earth element is the 1/3 of total amount, temperature Degree is 47 DEG C, incorporation time 50 seconds；
3rd stage：Negative pressure mixing plant sets negative pressure as 90mbar, and the addition of rare earth element is the 1/3 of total amount, temperature It is 44 DEG C, incorporation time 50 seconds.Always, stable quality is reliable for the degree of oxidation of lead powder that negative pressure is prepared, and meets production needs.
The negative pressure mixing plant is negative pressure and cream device.
The beneficial effects of the invention are as follows：Generation of the technology of the present invention with non-environmental-pollution, occupational hazards, the rare earth of preparation Red lead product quality is stablized, and is used for the production of accumulator, can improve the capacity of battery；Meanwhile the technique can be energy saving, Reduce enterprise's production cost, to enhance enterprise product the market competitiveness it is great environmental protection, ecology, economic benefit.
Specific implementation mode
The technical means, the creative features, the aims and the efficiencies achieved by the present invention is set to be easy to understand, with reference to Specific embodiment, the present invention is further explained.
Embodiment 1
A kind of lead-acid accumulator preparation method of rare earth red lead, steps are as follows：
S1. raw material lead is cut into lead, every block of bulk lead nearly weighs 4.5 kilograms, is placed in Shimadzu formula lead powder machine cylinder, allows Bulk lead constantly scrapes inner wall of rotary drum, avoids thin lead powder and is adhered on inner wall of rotary drum, to increase shot and inner wall of rotary drum Collision opportunity, increase lead powder yield, keep the oxidizability of lead powder consistent；
S2. the lead powder in Shimadzu formula lead-power machine is taken out, is sent into mixing plant, then Rare Earth Lanthanum is added in mixing plant (La), the weight ratio of lead powder and Rare Earth Lanthanum (La) is 100:1.8, it is stirred, is made containing dilute with 130 revs/min of rate The lead oxide powder of earth elements；
S3. cool down dedusting：By the lead oxide powder containing Rare Earth Lanthanum (La) of preparation by air-introduced machine through conveyance conduit, in a steady stream It is constantly introduced into bag filter, removes lead dust, evade the generation of occupational hazards；
S4. it is granulated：It will be sent into Granulation Equipments containing Rare Earth Lanthanum (La) lead oxide powder in deduster, temperature is heated up to 100 DEG C or so, it is granulated, prepares the graininess of 200 mesh or so；
S5. screening separation：The lead oxide powder particle containing Rare Earth Lanthanum (La) of preparation is screened, 200 mesh or so Particle is separated into next process, and the remaining undesirable granulating working procedure that returns to is granulated again；
S6. calcined oxide：The lead oxide powder containing rare earth element come will be screened out to put into red lead calcined oxide stove, Calcined oxide is carried out at a high temperature of 600 degrees centigrade, it is both rare earth red lead product to aoxidize product obtained；
S7. product inspection：By rare earth red lead made from calcined oxide, it is sampled chemical examination, red lead product should be met National sector standard【HG/T4503-2013】, the content of rare earth met again in product is greater than or equal to 1.5%, otherwise for not Qualified products；
S8. finished product packing：Examine qualified product to be packed using Tie Tong or container bag, can also be wanted to need according to client into Row packaging, storage are for sale.
Embodiment 2
A kind of lead-acid accumulator preparation method of rare earth red lead, steps are as follows：
S1. raw material lead is cut into lead, every block of bulk lead nearly weighs 4.5 kilograms, is placed in Shimadzu formula lead powder machine cylinder, allows Bulk lead constantly scrapes inner wall of rotary drum, avoids thin lead powder and is adhered on inner wall of rotary drum, to increase shot and inner wall of rotary drum Collision opportunity, increase lead powder yield, keep the oxidizability of lead powder consistent；
S2. the lead powder in Shimadzu formula lead-power machine is taken out, is sent into mixing plant, then rare earth member is added in mixing plant The weight ratio of element, lead powder and rare earth element is 100:1.8, it is stirred, is made containing rare earth member with 130 revs/min of rate The lead oxide powder of element；
S3. cool down dedusting：By the lead oxide powder containing rare earth element of preparation by air-introduced machine through conveyance conduit, in a steady stream not Disconnected is introduced into bag filter, removes lead dust, evades the generation of occupational hazards；
S4. it is granulated：It will be sent into Granulation Equipments containing rare earth element lead oxide powder in deduster, temperature is heated up to 100 DEG C Left and right, is granulated, and the graininess of 200 mesh or so is prepared；
S5. screening separation：The lead oxide powder particle containing rare earth element of preparation is screened, of 200 mesh or so Grain is separated into next process, and the remaining undesirable granulating working procedure that returns to is granulated again；
S6. calcined oxide：The lead oxide powder containing rare earth element come will be screened out to put into red lead calcined oxide stove, Calcined oxide is carried out at a high temperature of 600 degrees centigrade, it is both rare earth red lead product to aoxidize product obtained；
S7. product inspection：By rare earth red lead made from calcined oxide, it is sampled chemical examination, red lead product should be met National sector standard【HG/T4503-2013】, the content of rare earth met again in product is greater than or equal to 1.5%, otherwise for not Qualified products；
S8. finished product packing：Examine qualified product to be packed using Tie Tong or container bag, can also be wanted to need according to client into Row packaging, storage are for sale.
The rare earth element is lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), group more than one kind or two kinds of terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) and lutetium (Lu) It closes.
Mixing plant in the S2 steps is negative pressure mixing plant, and whipping step is divided into 3 stages completions：
1st stage：Negative pressure mixing plant sets negative pressure as 125mbar, and the addition of rare earth element is the 1/3 of total amount, temperature Degree is 50 DEG C, incorporation time 50 seconds；
2nd stage：Negative pressure mixing plant sets negative pressure as 105mbar, and the addition of rare earth element is the 1/3 of total amount, temperature Degree is 47 DEG C, incorporation time 50 seconds；
3rd stage：Negative pressure mixing plant sets negative pressure as 90mbar, and the addition of rare earth element is the 1/3 of total amount, temperature It is 44 DEG C, incorporation time 50 seconds.Always, stable quality is reliable for the degree of oxidation of lead powder that negative pressure is prepared, and meets production needs.
Rare earth red lead prepared by the embodiment of the present application 2 is used to prepare the plumbic acid electricity that lead-acid battery lead plaster is prepared with common lead plaster Pond proving and comparisom data are shown in Table 1；
Table 1
Such as, 12Ah lead-acid accumulators plate railings of anode and cathode does not become to be added in anode diachylon in other process conditions Rare earth red lead is assembled into 12V-12Ah accumulators progress contrast test with the pole plate that rare earth red lead is made is not added with：
12V-12Ah accumulator capacities are tested：
Volume test with national standard after lead accumulator full charge, with 2 hour rates, that is, 6.0A constant-current discharges to battery electricity Until being pressed onto 10.5V.
Not plus the battery discharge time of rare earth red lead releases 13.2Ah capacitances in 132 minutes；
The battery discharge time of rare earth red lead is added to release 15.5Ah capacitances in 155 minutes.
The two compares relative capacity amount and improves 21%.
The test of 12V-12Ah accumulator cell charging and discharging cycle lives：
It is a cycle that accumulator, which uses and is discharged to 10.5V with 2 hour rates i.e. 6.0A after current limliting constant-voltage charge to 14.8V,；
Not plus the accumulator cell charging and discharging cycle life of rare earth red lead is 286 times；
It is 560 times to add the accumulator cell charging and discharging cycle life of rare earth red lead；
Opposite charge and discharge circulation life improves 95% or more.
Accumulator added with rare earth red lead prepared by the application, heavy-current discharge performance are improved, battery Cost is reduced.
The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention.The technology of the industry Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its Equivalent thereof.

Claims (5)

1. a kind of lead-acid accumulator preparation method of rare earth red lead, it is characterised in that steps are as follows：
S1. raw material lead is cut into lead, every block of bulk lead nearly weighs 4.5 kilograms, is placed in lead powder machine cylinder, prepares lead powder；
S2. the lead powder in lead-power machine is taken out, is sent into mixing plant, then rare earth element is added in mixing plant, lead powder with it is dilute The weight ratio of earth elements is 100:1.8, it is stirred with 130 revs/min of rate, the lead oxide containing rare earth element is made Powder；
S3. cool down dedusting：By the lead oxide powder containing rare earth element of preparation by air-introduced machine through conveyance conduit, endlessly It is introduced into bag filter, removes lead dust, evade the generation of occupational hazards；
S4. it is granulated：It will be sent into Granulation Equipments containing rare earth element lead oxide powder in deduster, temperature is heated up to 100 DEG C, carries out It is granulated, prepares the graininess of 200 mesh；
S5. screening separation：The lead oxide powder particle containing rare earth element of preparation is screened, the particle point of 200 mesh or so It separates out to enter next process, the remaining undesirable granulating working procedure that returns to is granulated again；
S6. calcined oxide：The lead oxide powder containing rare earth element come will be screened out to put into red lead calcined oxide stove, Calcined oxide is carried out at a high temperature of 600 degrees centigrades, it is both rare earth red lead product to aoxidize product obtained；
S7. product inspection：By rare earth red lead made from calcined oxide, it is sampled chemical examination, the country of red lead product should be met Professional standard【HG/T4503-2013】, the content of rare earth met again in product is greater than or equal to 1.5%, is otherwise unqualified Product；
S8. finished product packing：It examines qualified product to be packed using Tie Tong or container bag, can also want to wrap according to client Dress, storage are for sale.
2. a kind of preparation method of lead-acid accumulator rare earth red lead according to claim 1, it is characterised in that：Described Rare earth element is the group of one kind or two kinds of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium or more It closes.
3. a kind of preparation method of lead-acid accumulator rare earth red lead according to claim 1, it is characterised in that：The S2 Mixing plant in step is negative pressure mixing plant, and whipping step is divided into 3 stages completions：
1st stage：Negative pressure mixing plant sets negative pressure as 125mbar, and the addition of rare earth element is the 1/3 of total amount, and temperature is 50 DEG C, incorporation time 50 seconds；
2nd stage：Negative pressure mixing plant sets negative pressure as 105mbar, and the addition of rare earth element is the 1/3 of total amount, and temperature is 47 DEG C, incorporation time 50 seconds；
3rd stage：Negative pressure mixing plant sets negative pressure as 90mbar, and the addition of rare earth element is the 1/3 of total amount, temperature 44 DEG C, incorporation time 50 seconds.
4. a kind of preparation method of lead-acid accumulator rare earth red lead according to claim 1, it is characterised in that：Described Negative pressure mixing plant is negative pressure and cream device.
5. a kind of preparation method of lead-acid accumulator rare earth red lead according to claim 1, it is characterised in that：The S1 Lead-power machine in step is Shimadzu formula lead-power machine.
CN201810235053.XA 2018-03-21 2018-03-21 A kind of preparation method of lead-acid accumulator rare earth red lead Withdrawn CN108598387A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102709549A (en) * 2012-05-08 2012-10-03 浙江天能电池江苏新能源有限公司 Tubular lead-acid battery positive pole squeezing cream and preparation method thereof
CN103708536A (en) * 2013-12-25 2014-04-09 界首市骏马工贸有限公司 Production technique for red lead containing rare earth
CN104241609A (en) * 2014-07-01 2014-12-24 超威电源有限公司 Vacuum paste mixing process of lead-acid power battery
CN105080418A (en) * 2015-08-03 2015-11-25 安徽新能电源科技有限公司 Lead-acid storage battery negative electrode plate negative pressure paste mixing technology
CN107487781A (en) * 2017-07-27 2017-12-19 朱可可 A kind of red lead production water law energy-conservation prilling

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102709549A (en) * 2012-05-08 2012-10-03 浙江天能电池江苏新能源有限公司 Tubular lead-acid battery positive pole squeezing cream and preparation method thereof
CN103708536A (en) * 2013-12-25 2014-04-09 界首市骏马工贸有限公司 Production technique for red lead containing rare earth
CN104241609A (en) * 2014-07-01 2014-12-24 超威电源有限公司 Vacuum paste mixing process of lead-acid power battery
CN105080418A (en) * 2015-08-03 2015-11-25 安徽新能电源科技有限公司 Lead-acid storage battery negative electrode plate negative pressure paste mixing technology
CN107487781A (en) * 2017-07-27 2017-12-19 朱可可 A kind of red lead production water law energy-conservation prilling

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Application publication date: 20180928