CN1619870A - Mercury-free zinc-manganese-carbon paste battery - Google Patents
Mercury-free zinc-manganese-carbon paste battery Download PDFInfo
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Abstract
The invention relates to a mercury-free zinc-manganese-carbon paste battery, the electrolyte of which is MgCl 2 、NH 4 Cl 2 Mainly comprises ZnCl 2 The three components are not distinguished by internal and external electrolytes, and each liter of the electrolyte contains the following substance MgCl in percentage by weight 2 11.0－16.0％，NH 4 Cl 12.0－14.0％，ZnCl 2 6.0 to 9.0 percent of water, and the balance of PVA 1.00 to 2.00g 3 0.20-0.40g, the specific weight of the electrolyte is 20-25 Baume degrees, and the pH value is 5.0-6.0. The battery uses mercury-free corrosion inhibitor, which is PVA and B (OH) 3 The boron alkoxide resin is mainly prepared by adding 16C or 18C trimethyl ammonium chloride or PVA and B (OH) 3 The generated boron alkoxide resin is taken as the main material and is supplemented with InCl 3 Or BiCl 3 The invention realizes the mercury-free battery by improving the electrolyte system and the corrosion-retarding technology, can greatly improve the discharge performance and the storage performance of the battery, and can solve the problem of waste batteries from the production sourceAnd (5) pollution to the environment.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a mercury-free zinc-manganese-carbon paste battery.
Background
Zinc-manganese batteries include two major types, namely zinc-manganese alkaline batteries and zinc-manganese-carbon batteries. Zinc manganese alkaline cells use KOH or NaOH as the electrolyte. NH for zinc-manganese-carbon battery 4 Cl and ZnCl 2 As electrolyte, zinc manganese carbon battery with NH 4 Cl or ZnCl 2 Two electrolyte systems are formed by different dosages, and the corresponding battery is called an ammonium battery or a zinc battery.
The zinc-manganese-carbon cylindrical battery has two structures, namely a paperboard structure and a paste structure. The battery with the paperboard structure uses pulp paper as an isolation layer. Starch, flour and corrosion inhibitor HgCl for paste type structure battery 2 Mixing with external electrolyte to obtain slurry, and heating the slurry gel in water bath at 70-90 deg.C to form an isolating layer (commonly called paste layer) during battery assembly.
Zinc manganese carbon paste batteries have been known for over a century since the invention. The battery has the advantages of simple structure, readily available materials, mature manufacture and good cost performance, is still the leading product in the battery market, nearly 300 hundred million of various batteries are produced in China, and nearly 50 percent of zinc-manganese carbon paste (ammonium) R20 batteries.
In the current zinc manganese carbon battery, the specific gravity of the electrolyte for the ammonium battery is 18.5-25.0 Baume degrees, and NH is used 4 Cl-based, NH thereof 4 Cl content of 22-24%, znCl 2 The content is 14-18%. Adding NH into the battery core powder of the ammonium battery 4 Cl solid 15-18%. Natural MnO suitable for ammonium battery 2 Powder, optionally electrolytic MnO 2 The powder improves electrical properties. The advantages of the ammonium battery are low cost, wide application, short service lifeThe circuit current is high, and the intermittent discharge is good. Its disadvantages are poor continuous discharge performance under heavy load, poor leakage resistance and poor low temperature resistance. The ammonium cell is adapted to the paste structure and also to the cardboard structure. Now, the R20 type, R14 type and R40 type batteries are basically paste type structures.
The electrolyte for zinc type battery has specific gravity of 28.0-32.5 baume degree and is ZnCl 2 Mainly of ZnCl 2 Content of NH 24-26% 4 The Cl content is 3-5%. Full-electrolytic MnO suitable for zinc type battery 2 The powder has good continuous discharge performance under heavy load, high output power, good leak resistance and good low temperature resistance. But the cell is, for example, of natural MnO 2 The powder, the battery performance will be degraded. The storage performance of the battery is unstable and depends particularly on the quality level of the assembly. The zinc type battery is not suitable for the paste type structure and is only suitable for the paperboard structure. The reason is high concentration of ZnCl 2 The slurry can be naturally gelled without being heated in a short time, and the slurry can not be discharged during the assembly of the battery.
One of the present inventors invented "magnesium-zinc environmental protection electrolyte". The specific gravity of the electrolyte is 21-23 baume degrees, and MgCl is contained in the electrolyte 2 16-18% of ZnCl 2 14-16% of NH 4 Cl accounts for 3-5%, and H is added into each liter of electrolyte 3 BO 3 2.00-3.00g and PVA2.00-3.00g. The electrolyte is MgCl 2 And ZnCl 2 Predominantly, NH 4 Cl is used as an auxiliary material to form three-component electrolyte, and the essence of the three-component electrolyte is improvement of zinc type electrolyte, and the three-component electrolyte is still not suitable for a paste structure but is suitable for a paperboard structure for the same reason as the zinc type electrolyte. If the relative concentration of the electrolyte is reduced for the paste structure, the short-circuit current of the battery is low, the storage is reduced quickly, and the zinc electrode is passivated early when the battery is discharged, so that the discharge rate is reduced.
The following can be recognized from the perspective of the cell reaction mechanism that the use of different types of electrolytes in the above zinc-manganese cell causes differences in the cell reaction:
the zinc-manganese cell is Zn as anode, mnO 2 As a cathode, the discharge mechanism is a proton electron mechanism.
An anode (-): (1)
and (2) a cathode (+): (2)
and (3) battery reaction: (3)
zinc-manganese alkaline cell:
using KOH or NaOH as the electrolyte, the cell reaction was as follows (alkaline conditions):
H + proton is formed by H 2 O is provided by dissociation in an alkaline medium.
Zinc-manganese-zinc type cell:
with ZnCl 2 Predominantly, NH 4 Cl is used as an auxiliary electrolyte, and the cell reaction is as follows:
the reaction product Zn (OH) Cl may be present in the form of a polyhydration. H + Proton is formed by ZnCl 2 Hydrolysis provides.
It features that the zinc-type cell consumes water.
As mentioned above, "magnesium-zinc environmental protection electrolyte", mgCl is used 2 And ZnCl 2 Predominantly, NH 4 Cl is used as an auxiliary electrolyte, and the cell reaction is as follows:
the reaction is the same as that of a zinc type battery in the early stage of discharge, namely:
late stage of discharge, mgCl 2 Participate in the hydrolysis reaction, namely:
H + protons not only formed from ZnCl 2 Provided by hydrolysis, and may also be provided by MgCl 2 Hydrolysis provides. MgCl 2 Zn participating in hydrolysis reaction in battery discharging process 2+ No increase in ion concentration, H + The proton consumption is increased and the pH of the electrolyte is increased. The cell reaction at this time was:
it can be seen that the magnesium-zinc environment-friendly electrolyte is used for a zinc-manganese-carbon battery, and the battery reaction characteristic is still water consumption, which is the same as that of a zinc-type battery.
Zinc-manganese-ammonium battery
By NH 4 Cl-based, znCl 2 As an auxiliary electrolyte, the cell reaction formula is as follows:
H + proton is formed by NH 4 Cl dissociation or hydrolysis. ZnCl 2 Present in excess of NH 4 In Cl, the hydrolysis reaction is inhibited by the complexation reaction.
It can be seen that the ammonium cell reaction is characterized by salt consumption.
The electrolyte of all the existing zinc-manganese-carbon paste batteries is prepared by dividing the electrolyte into an inner electrolyte and an outer electrolyte. The internal electrolyte is used for mixing the electric core powder at a Baume degree of 21-25. The external electrolyte is mixed by 9.8 Baume degree and 32 Baume degree electrolyte according to a proportion and is used for preparing slurry. ZnCl electrolyte with 9.8 baume degree 2 The content is low, and the product is used as a size mixing liquid; znCl electrolyte with 32 baume degrees 2 The content is high, the paste is used as a pasting liquid, the viscosity of the paste can be adjusted, and the paste is easy to naturally paste in summer.
In order to improve the storage performance and discharge efficiency of all the existing zinc-manganese batteries, hgCl is used for the zinc-manganese-carbon battery 2 As a corrosion inhibitor, hgO is used for the zinc-manganese alkaline battery. HgCl is not used in the zinc-manganese-carbon battery 2 As a corrosion inhibitor, the 'zinc can perforation' is easy to occur during the storage of the battery and the battery is easy to scrap. HgCl 2 Can form zinc amalgam with Zn to make the zinc cylinder slow corrosion. HgCl in battery 2 Is used according to the weight of 0.1-0.05 percent of the pulp. And HgCl 2 Belongs to a highly toxic substance, which not only destroys the ecological balance and pollutes the environment, but also leads people to have chronic mercury poisoning through the food chain. After people suffer from chronic mercury poisoning, metabolic dysfunction, hair loss, tooth looseness and absentmindedness can be caused, so that the health condition is reduced.
In order to meet the national strategy of sustainable development, the national nine ministries published 1997 "regulations on limiting the mercury content of battery products". The specification states that: according to the practical situation of the battery industry in China, low mercury is firstly realized, and finally mercury-free is realized. The low mercury standard is a mercury content of no more than 0.025% by weight of the cell. The specifications also require: "production of alkaline zinc-manganese battery with mercury content higher than 0.0001% of battery weight is prohibited at home from 1/2005". It is only the "final reach" requirement to specify when to achieve mercury free for a zinc manganese carbon cell.
In order to realize that the zinc-manganese battery has no mercury, technicians in the battery industry make a great deal of research on the selection of mercury-substituting reagents. The battery industry has developed the zinc-manganese-carbon paste R20 type battery twice, one time is 'adding aluminum zinc sheet', the other time is screening mercury-substituting reagent extensively, the result is all uncertain.
The currently proposed mercury-substituting reagents include bismuth compounds, indium compounds, hydroxyl groups, ethers and quaternary ammonium salts, and the application of the reagents to zinc-manganese alkaline batteries is reported, but the application of the reagents to zinc-manganese carbon paste batteries is not reported.
BiCl for mercury-free R6 type paperboard batteries reported by Guangzhou Battery factories 3 As corrosion inhibitor, the perforation rate of the zinc cylinder can reach more than 30 percent when the battery is stored for three months.
No mercury test was conducted on the conventional ammonium R20 paste battery, and the perforation rate of the zinc can of the battery stored at normal temperature for three months was more than 30% regardless of the blank sample and the comparative sample. For the traditional ammonium R14 paperboard battery, certain four kinds of domestic mercury-free paper pulp layers are used for testing, and the perforation rate of the zinc cylinder can reach more than 50 percent after the battery is stored for three months. It is seen that it is difficult to achieve mercury free zinc manganese carbon ammonium batteries, whether in paste or cardboard construction.
In 89 years, the boron alkoxide resin is innovatively provided as an additive for zinc-manganese mercury batteries such as R6 and R03. Boron alkoxide resin is composed of B (OH) 3 The PVA is synthesized, and the generation of the PVA is related to material ratio, feeding sequence, dissolving temperature and acidity. The using method and the using amount are related to the electrolyte system. The boron alkoxide resin can reduce apparent humidity of the cell powder, increase water-containing capacity of the cell, enhance buffer capacity of the electrolyte, improve discharge efficiency and enable Hg 2+ 、Bi 3+ 、 In 3+ The plasma is uniformly replaced on the surface of the zinc, and the corrosion resistance of the zinc cylinder is improved.
Disclosure of Invention
The invention aims to solve the problems of the existing mercury-free zinc-manganese-carbon paste battery, particularly the R14 type and R20 type batteries in the aspects of realizing mercury-free performance and the like, and provides a mercury-free zinc-manganese-carbon paste battery which realizes mercury-free performance of the battery through improvement and innovation of an electrolyte system and a corrosion-retarding technology, can greatly improve the discharge performance and the storage performance of the battery, and can solve the problem of environmental pollution caused by waste batteries from a production source.
The technical scheme of the invention is as follows:
the structure of the mercury-free zinc-manganese-carbon paste battery comprises a zinc cylinder, a carbon rod, a battery core, a paste layer, a wax paper ring, a sealing layer, a battery cover, a copper cap, bottom wrapping paper and a bottom circle, and the mercury-free zinc-manganese-carbon paste battery keeps the basic structure of the existing zinc-manganese-carbon paste battery.
The innovation of the invention is that the same electrolyte is adopted for preparing the electric core powder and the slurry in the aspect of selection of the electrolyte and the corrosion inhibitor, and the electrolyte is an innovation without distinguishing the internal electrolyte from the external electrolyte. The electrolyte is MgCl 2 、 NH 4 Cl 2 Mainly comprises ZnCl 2 The electrolyte consists of three components, wherein each liter of electrolyte contains the following substances in percentage by weight:
MgCl 2 11.0-16.0％
NH 4 Cl 12.0-14.0％
ZnCl 2 6.0-9.0% of water as the rest;
additionally adding:
PVA 1.00-2.00g
B(OH) 3 0.20-0.40g
the electrolyte has a specific gravity of 20-25 Baume degree and a pH of 5.0-6.0, and PVA and B (OH) in the electrolyte 3 Is added as one of the main components of the corrosion inhibitor.
The mercury-free corrosion inhibitor used by the battery is divided into a first corrosion inhibitor and a second corrosion inhibitor, and is respectively suitable for different objects:
the first seed is PVA and B (OH) 3 The boron alkoxide resin is prepared mainly and supplemented with 16C or 18C trimethyl ammonium chloride, and the use method is to take the prepared boron alkoxide resinAdding 1.50-2.00g of 16C or 18C trimethyl ammonium chloride into one liter of the electrolyte, and dissolving at normal temperature for preparing slurry. Only suitable for adding electrolytic MnO to A 2 Powdered zinc manganese carbon paste batteries and zinc manganese carbon paperboard batteries.
The second kind is PVA and B (OH) 3 The generated boron alkoxide resin is taken as the main material and is supplemented with InCl 3 Or BiCl 3 The use method is to add InCl into each liter of prepared electrolyte 3 0.15-0.20g or BiCl 3 0.20-0.30g for preparing slurry. Natural MnO suitable for B species 2 Powder and additive electrolytic MnO 2 The powdered zinc-manganese-carbon paste battery and the powdered paperboard battery have wider application range than the battery A.
The electrolyte system is different from a zinc type or ammonium type double-component electrolyte system used by the traditional zinc-manganese-carbon paste battery and is also different from a magnesium-zinc environment-friendly electrolyte system, has good conductivity and improved weather resistance, has a corrosion inhibition effect on a zinc electrode, has relatively lower material cost, and is suitable for being used as a mercury-free zinc-manganese-carbon paste battery by using all-natural manganese powder.
MgCl is used in the invention 2 And NH 4 Cl as main material and ZnCl as auxiliary material 2 The three-component electrolyte system has the following battery reaction formula:
in the early stage of discharge as in an ammonium cell, i.e.
Later discharge with Zn 2+ Increase in ion concentration, H + Proton consumption, increase of electrolyte pH, mgCl 2 Hydrolysis occurs and the cell reaction is as follows:
the electrolyte system is used for the zinc-manganese-carbon battery, and the battery reaction characteristic is that salt and water are consumed.
The reaction can be described by active material theoretical capacity matching, battery leakage-proof performance and load voltage discharge time fraction of each stage in the battery discharge process.
Taking R20 type as an example, conventional ammonium battery NH 4 The amount of Cl is MnO 2 The theoretical capacity is 1-2 times, and the battery only accounts for 50-65%.
The leakage of the battery is prevented by 0.6V when the continuous discharge of 3.9 omega is stopped, the leakage-proof rate of the traditional ammonium battery is less than or equal to 100 percent, and the battery of the invention is 100 percent. The leakage is prevented by 0.35V when the continuous discharge of 3.9 omega is stopped, the leakage rate of the ammonium battery can reach more than 20 percent, and the invention is 0 percent.
0.9V after 3.9 omega continuous discharge, all natural manganese powder, 42g net weight of a battery core, 220-240 minutes of discharge time of the traditional ammonium battery and 240-260 minutes of the battery.
TABLE 1 fractional discharge time of load voltage at each stage
| Initial voltage-1.20V | 1.20-1.00V | 1.00-0.9V | |
| Ammonium R20 type | 20％ | 57％ | 23％ |
| R20 type of the present invention | 20％ | 45％ | 35％ |
Discharge time fraction = (discharge time at a certain voltage/end 0.9V discharge time) × 100%
The battery has more stable discharging process and longer discharging time. The above facts support the discharge reaction of the cell of the present invention.
The invention uses PVA and B (OH) 3 The composite is supplemented with quaternary ammonium salt to form a compound corrosion inhibitor, so that the battery has no mercury and the discharge rate of the battery can be improved. The PVA and boron compound composition has characteristic adsorption effect on the zinc electrode due to the electron deficiency of boron, and after the battery is discharged, a layer of silvery white bright substance is presented on the inner wall surface of the zinc cylinder, which is an electron discharge product Zn of zinc + ·enH 2 As a result of the surface behavior of O and the composition, the O is separated from the zinc electrode matrix and is easy to react with H + The protons react directly to form hydrogen, and this phenomenon is improved and zinc is more fully dissolved using quaternary ammonium salts. Therefore, the composite corrosion inhibitor has characteristic adsorption and desorption actions on the zinc electrode, the adsorption is favorable for overcoming the perforation of the zinc cylinder when the battery is stored, and the desorption is favorable for improving the discharge rate of the battery.
And PVA and B (OH) 3 The composition is supplemented with InCl 3 Or BiCl 3 A compound corrosion inhibitor is formed,Bi 3+ or In 3+ Also can inhibit Zn + ·e nH 2 O and H + Protons react directly because of Bi 3+ Or In 3+ Is a high hydrogen overpotential substance capable of being replaced on the surface by Zn, PVA and B (OH) 3 The composition enables Bi 3+ Or In 3+ The zinc can is more uniformly replaced on the inner wall of the zinc can, so that the perforation of the zinc can is favorably overcome when the battery is stored, the passivation phenomenon is favorably overcome when the battery is discharged, and the discharge rate is improved.
In addition, the invention also improves the specification and the size of the battery cell, taking the R20 type as an example, and comparing with the traditional R20 type as follows:
table 2 cell specification and dimension comparison table
| Traditional electric core | The invention electric core | |
| Electric core net weight (g) | 43.5-44.5 | 42.0-43.0 |
| Diameter of electrical core (mm) | 27.3-27.6 | 26.5-26.8 |
| Shoulder height of electrical core (mm) | 39.5-40.5 | 42.5-43.5 |
| Core water content (%) | 18.5-19.5 | 21.5-22.5 |
The reduction of the diameter of the battery cell is beneficial to the battery cell entering into the cylinder and reduces the hanging damage and pollution of the battery cell to the zinc cylinder. The diameter of the battery core is reduced, the paste thickness is increased, and the paste capacity is increased. The increase of the paste thickness increases the resistance of impurities in the battery cell to migrate to the inner wall of the zinc cylinder, thereby being beneficial to the corrosion resistance of the zinc cylinder. The increase of the paste capacity has the action of inhibiting salt supersaturation crystallization caused by air temperature and can also improve the liquid leakage behavior of gel collapse.
The increase of the shoulder height of the battery core can increase the reaction area of the counter electrode, so that the short-circuit current of the battery is increased, and the discharge efficiency is increased. The shoulder height dimension of the battery core set by the original process can be increased due to the slurry absorption of the battery core, and the slurry absorption easily causes the structure of the battery core to be loosened and the short-circuit current of the battery to be reduced. The battery cell has high water content and molding density of more than 2.00g/cm, and the battery cell is not easy to absorb slurry, so the shoulder height size of the battery cell can be increased.
The water content of the traditional battery cell is 18.5-19.5%, if the ratio of Mn to C = 87: 13, the battery cell is difficult to form, and generally the ratio of Mn to C = 86: 14 or 85: 15 is taken. Mn means MnO 2 Powder, C means acetylene black.
The battery cell of the invention contains 21.5-22.5% of water, mn: C = 87: 13,the cell formation was good because the magnesium chloride was MgCl 2 ·6H 2 The existence of the O form and the reduction of the apparent humidity of the cell powder by the boron alkoxide resin.
The invention has the following characteristics:
1. the battery electrolyte system adopts MgCl 2 And NH 4 Cl as main material and ZnCl as auxiliary material 2 The three-component system is an improvement on the ammonium battery. It can be used for battery with paste structure, or battery with paperboard structure, and can use natural MnO 2 The reaction of the powder consumes salt and water, the battery discharge process is more stable, and the discharge time is longer. The discharge capacity of the battery can be improved by more than 8 percent when the battery is continuously discharged to 0.9V from 3.9 omega; the leakage is prevented when the battery is continuously discharged to 0.35V at the voltage of 3.9 omega, the leakage rate is 0 percent, and the leakage rate of the traditional ammonium battery is more than 20 percent. The reason is that the battery consumes water in the reaction mechanism, so that the battery is not easy to leak.
2. The electrolyte system adopted by the battery can be used for mixing powder and preparing slurry, no internal and external electrolyte is distinguished, the slurry does not have a natural gelatinization phenomenon, the process is simplified in the production process, and the production efficiency is improved.
3. The battery of the invention adopts a unique mercury-free corrosion inhibitor formula, has obvious corrosion inhibition effect, and the traditional zinc-manganese-carbon paste type ammonium battery uses a mercury-substitute reagent InCl 3 、BiCl 3 Or quaternary ammonium salt, and the battery can be stored for three months, and the perforation rate of the battery zinc cylinder can reach 30-50%. The battery of the invention can be stored for more than two years at normal temperature, and the battery can be stored for 45 days at high temperature and high humidity without the perforation of the zinc cylinder, so that the mercury-free zinc-manganese-carbon paste battery can be completely realized, and the discharge rate of the battery can be improved.
4. The battery reduces environmental pollution after being mercury-free, is beneficial to environmental protection, and conforms to the national environmental protection policy and sustainable development strategy.
5. The basic structure of the battery is not changed, the manufacturing process which is basically the same as the traditional battery production process flow can be adopted, the process operation procedures are basically the same, and the battery is suitable for assembling domestic battery production equipment.
6. The battery core specification and size of the battery can be improved, and the assembly quality and the rate of qualified products of the battery can be improved.
7. The cell of the invention can reduce the cost, taking mercury-free R20S as an example, 10kg of zinc and 15kg of ZnCl can be consumed less for every ten thousand cells 2 The saving value is 150-180 yuan/ten thousand.
The applicant detects the mercury-free zinc-manganese-carbon paste battery (mercury-free R20S battery) through the national light industrial battery quality supervision and detection center, and the detection conclusion is as follows: all indexes reach GB/T7112-1998 technical requirements and the national standard of mercury-free batteries. The detected mercury content was 3X 10 -6 % lower than standard of mercury-free battery 1 × 10 -4 % of two orders of magnitude.
Drawings
Fig. 1 is a structural view of the mercury-free zinc manganese carbon paste battery.
Detailed Description
The structure of the mercury-free zinc-manganese-carbon paste battery is the same as that of the existing non-wrapped non-bundled battery, and the mercury-free zinc-manganese-carbon paste battery is shown in a figure 1, wherein: "+" -anode extreme, "-" -cathode extreme, "-1-copper cap, 2-battery cap, 3-sealing layer, 4-wax paper ring, 5-carbon rod, 6-electric core, 7-paste layer, 8-zinc cylinder, 9-wrapping paper, 10-plastic bottom circle.
The following describes the preparation of a mercury-free zinc-manganese carbon paste battery
Example 1: non-wrapping and non-rolling preparation process of mercury-free zinc-manganese carbon R20S paste battery
1. Electrolyte formulation
Per liter of electrolyte:
MgCl 2 ·6H 2 O 13.5％
NH 4 Cl 12.0％
ZnCl 2 8.0％
balance of water
Additionally adding: PVA 1.50g
B(OH) 3 0.30g
Specific gravity of electrolyte is 21.5-22.5 baume degree
The pH value of the electrolyte is 5.0-6.0
2. Slurry formulation
Adjusting slurry per liter:
total salt 26.5%
21.5 percent of powder material
Balance of water
Additionally adding: inCl 3 0.15g
PVA 1.50g
B(OH) 3 0.30g
3. Battery cell formula
Manganese to carbon ratio of 87: 13 (natural MnO) 2 )
Addition of NH 4 Cl 13% (based on the total weight of manganese and carbon)
Cell moisture 21.5-22.5% (based on the weight of cell powder)
4. Cell specification
The net weight of the electric core powder is 42.0-42.5g
Cell diameter 26.5mm
Cell shoulder height 42.0 - 42.5mm
The molding density of the battery core is more than or equal to 2.00g/ml
5. Battery pasting
The slurry suction time is 2 to 4 minutes
The gelatinization temperature is 85-90 deg.C
Pasting time is 1-2 minutes
6. Otherwise the same as the traditional battery technology
7. Performance of battery
Open circuit voltage 1.580V
Short-circuit current of 6.5-7.8A
The comprehensive performance conforms to the GB/T7112-1998 standard
Example 2: non-wrapping and non-rolling preparation process of mercury-free zinc-manganese carbon R14S paste battery
1. Electrolyte formulation
Per liter of electrolyte:
MgCl 2 ·6H 2 O 14.5％
NH 4 Cl 13.0％
ZnCl 2 9.0％
balance of water
Additionally adding: PVA 1.50g
B(OH) 3 0.30g
Specific gravity of the electrolyte is 21.5-22.5 Baume degree
The pH value of the electrolyte is 5.0-6.0
2. Slurry formulation
Adjusting slurry per liter:
total salt 27.5%
22.5 percent of powder material
Balance of water
Additionally adding: biCl 3 0.20g
PVA 1.50g
B(OH) 3 0.30g
3. Battery cell formula
Manganese to carbon ratio of 87: 13 (in which MnO is electrolyzed) 2 20％)
Addition of NH 4 Cl13% (based on the total weight of manganese and carbon)
The moisture of the battery cell is 20.5-21.5% (based on the weight of the battery cell powder material)
As a reference)
4. Cell specification
The net weight of the electric core powder is 16.0-16.5g
Cell diameter 19.5mm
The height of the shoulder of the battery core is 32.5-33.5mm
The molding density of the battery core is more than or equal to 2.00g/ml
5. Battery pasting
The slurry suction time is 2 to 4 minutes
The gelatinization temperature is 85-90 deg.C
Pasting time is 1-2 minutes
6. Otherwise the same as the traditional battery technology
7. Performance of battery
Open circuit voltage 1.65V
Short-circuit current of 5.0-6.5A
The comprehensive performance conforms to the GB/T7112-1998 standard
Example 3: mercury-free zinc-manganese carbon R6 paperboard battery
1. Electrolyte formulation
Per liter of electrolyte:
MgCl 2 ·6H 2 O 13.5％
NH 4 Cl 13.0％
ZnCl 2 9.0％
balance of water
Additionally adding: PVA 1.50g
B(OH) 3 0.30g
16C Trimethylammonium chloride 2.0g
Specific gravity of electrolyte is 21.5-22.5 baume degree
The pH value of the electrolyte is 5.0-6.0
2. Battery cell formula
Manganese carbon 87: 13 (in which MnO is electrolyzed) 2 25％)
Addition of NH 4 Cl13% (based on the total weight of manganese and carbon)
Cell moisture 21.5-22.5% (based on the weight of cell powder)
3. Cell specification
The net weight of the electric core powder is 7.6-7.8g
The height of the shoulder of the battery core is 34.0-35.0mm
The molding density of the battery core is more than or equal to 2.00g/ml
4. Otherwise the same as the traditional battery technology
5. Performance of battery
Open circuit voltage 1.65V
Short-circuit current of 4.5-5.5A
The comprehensive performance conforms to the GB/T7112-1998 standard
Example 4: preparation process of mercury-free zinc-manganese-carbon R20S paste type battery wrapping paper binding wire
1. Electrolyte formulation
Per liter of electrolyte:
MgCl 2 ·6H 2 O 15.2％
NH 4 Cl 13.4％
ZnCl 2 8.1％
PVA 2.00g
B(OH) 3 0.40g
the balance of water
Specific gravity of the electrolyte is 23.0-23.5 baume degree
The pH value of the electrolyte is 5.0-6.0
2. Slurry formulation
Adjusting slurry per liter:
total salt 25.8%
20.7 percent of powder material
Balance of water
Additionally adding: PVA2.00 g
B(OH) 3 0.40g
18C Trimethylammonium chloride 2.00g
3. Battery cell formula
Manganese to carbon ratio of 87: 13 (in which MnO is electrolyzed) 2 20％)
Addition of NH 4 Cl15% (based on the total weight of manganese and carbon)
The moisture content of the cell is 16.5-17.5% (based on the weight of the cell powder material)
As a reference)
4. Battery cell specification
The net weight of the electric core powder is 42.5-43.0g
Cell diameter 27.0mm
The shoulder height of the battery core is 40.0-41.0mm
The molding density of the battery core is more than or equal to 2.10g/ml
5. Battery pasting
The slurry suction time is 5 to 6 minutes
The gelatinization temperature is 85-90 deg.C
Pasting time is 1-2 minutes
6. Otherwise the same as the conventional battery process
7. Performance of battery
Open circuit voltage 1.680V
Short-circuit current of 7.5-8.5A
The comprehensive performance conforms to the GB/T7112-1998 standard
Claims (1)
1. Mercury-free zinc-manganese-carbon paste type battery, which comprises a zinc barrel, a carbon rod, an electric core, a paste layer, a wax paper ring, a sealing layer, a battery cover, a copper cap, bottom wrapping paper and a bottom circle, and is characterized in that: the same electrolyte is adopted for preparing the core powder of the electric core and the slurry of the slurry paste layer, no internal and external electrolyte is distinguished, and the electrolyte is MgCl 2 、 NH 4 Cl 2 Mainly comprises ZnCl 2 The electrolyte contains the following substances in percentage by weight per liter:
MgCl 2 11.0-16.0％
NH 4 Cl 12.0-14.0％
ZnCl 2 6.0-9.0% of water as the rest;
additionally adding:
PVA 1.00-2.00g
B(OH) 3 0.20-0.40g
the specific gravity of the electrolyte is 20-25 Baume degrees, and the PH value is 5.0-6.0;
the battery uses mercury-free corrosion inhibitor, which is PVA and B (OH) 3 The generated boron alkoxide resin is taken as a main material, 16C or 18C trimethyl ammonium chloride is added as an auxiliary material, and 1.50-2.00g of 16C or 18C trimethyl ammonium chloride is added into each liter of prepared electrolyte;
or, boron alkoxide resin generated by PVA and B (OH) 3 is taken as the main material, and InCl is taken as the auxiliary material 3 Or BiCl 3 The addition amount is that InCl is added into per liter of prepared electrolyte 3 0.15-0.20g or BiCl 3 0.20-0.30g。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410087841 CN1257571C (en) | 2003-10-26 | 2004-10-22 | Mercury-free zinc-manganese-carbon paste battery |
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| Application Number | Priority Date | Filing Date | Title |
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| CN200320103694 | 2003-10-26 | ||
| CN200320103694.9 | 2003-10-26 | ||
| CN 200410087841 CN1257571C (en) | 2003-10-26 | 2004-10-22 | Mercury-free zinc-manganese-carbon paste battery |
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| Publication Number | Publication Date |
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| CN1619870A true CN1619870A (en) | 2005-05-25 |
| CN1257571C CN1257571C (en) | 2006-05-24 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 200410087841 Expired - Fee Related CN1257571C (en) | 2003-10-26 | 2004-10-22 | Mercury-free zinc-manganese-carbon paste battery |
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| CN (1) | CN1257571C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101924223B (en) * | 2009-06-17 | 2012-11-28 | 广州市虎头电池集团有限公司 | Mercury-free full-anti-paste zinc-manganese battery |
| CN109616677A (en) * | 2018-12-10 | 2019-04-12 | 杭州长命电池有限公司 | Paste-type mercury-free battery slurry and preparation method thereof |
| CN110581286A (en) * | 2018-06-09 | 2019-12-17 | 广东三七新能源有限公司 | Mercury-free dry battery |
-
2004
- 2004-10-22 CN CN 200410087841 patent/CN1257571C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101924223B (en) * | 2009-06-17 | 2012-11-28 | 广州市虎头电池集团有限公司 | Mercury-free full-anti-paste zinc-manganese battery |
| CN110581286A (en) * | 2018-06-09 | 2019-12-17 | 广东三七新能源有限公司 | Mercury-free dry battery |
| CN109616677A (en) * | 2018-12-10 | 2019-04-12 | 杭州长命电池有限公司 | Paste-type mercury-free battery slurry and preparation method thereof |
| CN109616677B (en) * | 2018-12-10 | 2020-11-10 | 杭州长命电池有限公司 | Paste-type mercury-free battery slurry and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1257571C (en) | 2006-05-24 |
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