阅读说明：本技术 一种电流高利用率碳性锌锰干电池及其制造工艺 (Carbon zinc-manganese dry battery with high current utilization rate and manufacturing process thereof ) 是由 王嘉军 王文周 于金华 马忠红 于 2020-06-15 设计创作，主要内容包括：本发明属于碳性电池领域,公开了一种电流高利用率碳性锌锰干电池,包括负极锌筒、电解质浆料、碳棒、设置在复合正极与负极锌筒之间的隔膜和组合帽,所述电解质重量份数的成份：二氧化锰60-80份、碳材料8-10份、氯化铵5-7份、氯化锌4-6份、缓冲剂1-2份、改性添加剂1-2份和余量水。本发明制得的碳性锌锰干电池,相对现有技术的碳性电池,电池析氢量低,从而降低内阻,提高电池电流利用率,具有优异的放电容量,通过本发明制得的电解质浆料可提升碳性锌锰干电池的导电性能,进而提高电流利用率,通过改性添加剂,增强碳材料吸附电荷的性能,并促进二氧化锰对氢气的吸收,增强电池在大电流条件下的使用性能,进而延长电池的使用寿命和电池容量。(The invention belongs to the field of carbon batteries, and discloses a carbon zinc-manganese dioxide dry battery with high current utilization rate, which comprises a negative electrode zinc cylinder, electrolyte slurry, a carbon rod, a diaphragm and a combined cap, wherein the diaphragm and the combined cap are arranged between a composite positive electrode and the negative electrode zinc cylinder, and the electrolyte comprises the following components in parts by weight: 60-80 parts of manganese dioxide, 8-10 parts of carbon material, 5-7 parts of ammonium chloride, 4-6 parts of zinc chloride, 1-2 parts of buffering agent, 1-2 parts of modified additive and the balance of water. Compared with the carbon battery in the prior art, the carbon zinc-manganese dry battery prepared by the invention has low hydrogen evolution amount, thereby reducing internal resistance, improving the current utilization rate of the battery and having excellent discharge capacity.)

1. A carbon zinc-manganese dry battery with high current utilization rate is characterized in that: the composite anode comprises a cathode zinc cylinder, electrolyte slurry, a carbon rod, a diaphragm and a combined cap, wherein the diaphragm and the combined cap are arranged between a composite anode and the cathode zinc cylinder, and the electrolyte comprises the following components in parts by weight: 60-80 parts of manganese dioxide, 8-10 parts of carbon material, 5-7 parts of ammonium chloride, 4-6 parts of zinc chloride, 1-2 parts of buffering agent, 1-2 parts of modified additive and the balance of water.

2. The high current utilization zinc-manganese carbon dry cell of claim 1, wherein: the electrolyte comprises the following components in parts by weight: 60 parts of manganese dioxide, 8 parts of carbon material, 5 parts of ammonium chloride, 4 parts of zinc chloride, 1 part of buffering agent, 1 part of modified additive and the balance of water.

3. The high current utilization zinc-manganese carbon dry cell of claim 1, wherein: the electrolyte comprises the following components in parts by weight: 70 parts of manganese dioxide, 9 parts of carbon material, 6 parts of ammonium chloride, 5 parts of zinc chloride, 1.5 parts of buffering agent, 1.5 parts of modified additive and the balance of water.

4. The high current utilization zinc-manganese carbon dry cell of claim 1, wherein: the electrolyte comprises the following components in parts by weight: 80 parts of manganese dioxide, 10 parts of carbon material, 7 parts of ammonium chloride, 6 parts of zinc chloride, 2 parts of buffering agent, 2 parts of modified additive and the balance of water.

5. The high current utilization zinc-manganese carbon dry cell of claim 1, wherein: the preparation method of the modified additive comprises the following steps:

1) the additive is prepared by using a graphite rod as an electric arc method, wherein the cathode and the anode of 2 graphite rods are oppositely placed in a reaction medium, and high-voltage current of 1.5 kiloamperes is introduced for direct current electric arc discharge to prepare an anode product of the graphite rod, namely the additive.

2) The prepared additive is put into a constant temperature area of a quartz tube, is heated to 800-1200 ℃ after being filled with water, and then is reacted for 18-36h by applying a voltage of 300-500V to obtain the modified additive.

6. The high current utilization zinc-manganese carbon dry cell of claim 1, wherein: the manganese dioxide is alpha-MnO₂And the buffer is ammonium acetate.

7. The high current utilization zinc-manganese carbon dry cell of claim 1, wherein: the carbon material is one of conductive carbon black, expanded graphite, carbon nanotubes, graphene and carbon fibers.

8. A manufacturing process of a carbon zinc-manganese dioxide dry battery with high current utilization rate is characterized by comprising the following steps:

step 1, adding ammonium chloride, zinc chloride and a buffer agent into a stirring container, and fully stirring and mixing to form a pasty mixture;

step 2, adding a carbon material, manganese dioxide powder and a certain mass percent of modified additive into the pasty mixture prepared in the step 1, stirring at a high speed for 1-2 hours in a vacuum environment to obtain electrolyte slurry, and aging the obtained electrolyte slurry for more than 24 hours;

and 3, sleeving diaphragm paper on the inner wall of the negative electrode zinc cylinder, injecting aged electrolyte slurry with the filling amount being 1/2-4/5 of the height of the zinc cylinder, inserting a carbon rod as a current collector, coating sealing glue, adding a combined cap, and performing edge rolling and sealing on a machine to obtain the carbon zinc-manganese dry battery.

Technical Field

The invention relates to the technical field of carbon batteries, in particular to a carbon zinc-manganese dry battery with high current utilization rate and a manufacturing process thereof.

Background

Carbon batteries are all called: a neutral zinc-manganese dioxide dry battery (zinc-manganese dioxide dry battery) belongs to a primary battery in a chemical power supply and is a disposable battery. This chemical power supply device is also called a dry battery because its electrolyte is an immobile paste.

The electrolysis of zinc releases hydrogen which increases the internal resistance of the cell, and manganese dioxide mixed with graphite absorbs hydrogen; however, if the battery works continuously or is used for too long, the manganese dioxide is too late or is nearly saturated and incapable of absorbing the capacity again, and the battery loses the function because the output current is too small due to too large internal resistance.

Disclosure of Invention

Technical problem to be solved

1. Technical problem to be solved

Aiming at the problems in the prior art, the invention aims to provide a carbon zinc-manganese dry battery with high current utilization rate and a manufacturing process thereof, and solves the problems of low current utilization rate, poor conductivity and short service life of the carbon zinc-manganese dry battery commonly used at present.

(II) technical scheme

In order to achieve the purpose, the invention provides the following technical scheme:

the utility model provides a high utilization rate of electric current carbon nature zinc-manganese dioxide dry battery, includes negative pole zinc section of thick bamboo, electrolyte thick liquids, carbon-point, sets up diaphragm and the combination cap between compound positive pole and negative pole zinc section of thick bamboo, the composition of electrolyte weight parts: 60-80 parts of manganese dioxide, 8-10 parts of carbon material, 5-7 parts of ammonium chloride, 4-6 parts of zinc chloride, 1-2 parts of buffering agent, 1-2 parts of modified additive and the balance of water.

Preferably, the electrolyte comprises the following components in parts by weight: 60 parts of manganese dioxide, 8 parts of carbon material, 5 parts of ammonium chloride, 4 parts of zinc chloride, 1 part of buffering agent, 1 part of modified additive and the balance of water.

Preferably, the electrolyte comprises the following components in parts by weight: 70 parts of manganese dioxide, 9 parts of carbon material, 6 parts of ammonium chloride, 5 parts of zinc chloride, 1.5 parts of buffering agent, 1.5 parts of modified additive and the balance of water.

Preferably, the electrolyte comprises the following components in parts by weight: 80 parts of manganese dioxide, 10 parts of carbon material, 7 parts of ammonium chloride, 6 parts of zinc chloride, 2 parts of buffering agent, 2 parts of modified additive and the balance of water.

Preferably, the preparation method of the modified additive comprises the following steps:

1) the additive is prepared by using a graphite rod as an electric arc method, wherein the cathode and the anode of 2 graphite rods are oppositely placed in a reaction medium, and high-voltage current of 1.5 kiloamperes is introduced for direct current electric arc discharge to prepare an anode product of the graphite rod, namely the additive.

2) The prepared additive is put into a constant temperature area of a quartz tube, is heated to 800-1200 ℃ after being filled with water, and then is reacted for 18-36h by applying a voltage of 300-500V to obtain the modified additive.

Preferably, the manganese dioxide is alpha-MnO₂And the buffer is ammonium acetate.

Preferably, the carbon material is one of conductive carbon black, expanded graphite, carbon nanotubes, graphene and carbon fibers.

Another technical problem to be solved by the present invention is to provide a manufacturing process of a carbon zinc-manganese dioxide dry battery with high current utilization rate, which comprises the following steps:

step 1, adding ammonium chloride, zinc chloride and a buffer agent into a stirring container, and fully stirring and mixing to form a pasty mixture;

step 2, adding a carbon material, manganese dioxide powder and a certain mass percent of modified additive into the pasty mixture prepared in the step 1, stirring at a high speed for 1-2 hours in a vacuum environment to obtain electrolyte slurry, and aging the obtained electrolyte slurry for more than 24 hours;

and 3, sleeving diaphragm paper on the inner wall of the negative electrode zinc cylinder, injecting aged electrolyte slurry with the filling amount being 1/2-4/5 of the height of the zinc cylinder, inserting a carbon rod as a current collector, coating sealing glue, adding a combined cap, and performing edge rolling and sealing on a machine to obtain the carbon zinc-manganese dry battery.

(III) advantageous effects

Compared with the prior art, the invention provides a carbon zinc-manganese dioxide dry battery with high current utilization rate and a manufacturing process thereof, and the carbon zinc-manganese dioxide dry battery has the following beneficial effects:

(1) compared with the carbon battery in the prior art, the carbon zinc-manganese dry battery prepared by the invention has low hydrogen evolution amount, thereby reducing internal resistance, improving the current utilization rate of the battery and having excellent discharge capacity.

(2) The electrolyte slurry prepared by the invention can improve the conductivity of the carbon zinc-manganese dry battery, further improve the current utilization rate, enhance the performance of the carbon material for adsorbing charges, promote the absorption of manganese dioxide to hydrogen, enhance the service performance of the battery under the condition of large current, and further prolong the service life and the capacity of the battery.

(3) By adding weak acid and weak base salt into the electrolyte slurry, excessive H is generated during continuous discharge⁺Weak acid roots of the buffer substance are combined into weak acid which is difficult to ionize, thereby reducing H generated in the continuous discharge reaction⁺Concentration, no obvious change in pH of the cell, and H suppression⁺Reduction to H₂The amount of the electrolyte reduces the hydrogen evolution amount of the battery, reduces the internal resistance, improves the current utilization rate and enhances the conductivity.

In conclusion, the carbon zinc-manganese dioxide dry battery has the advantages of good conductivity, high current utilization rate, high working efficiency, long service life and large capacity.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The first embodiment is as follows:

the utility model provides a high utilization rate of electric current carbon nature zinc-manganese dioxide dry battery, includes negative pole zinc can, electrolyte thick liquids, carbon-point, sets up diaphragm and combination cap between compound positive pole and negative pole zinc can, and the electrolyte includes the composition of following parts by weight: 60 parts of manganese dioxide, 8 parts of carbon material, 5 parts of ammonium chloride, 4 parts of zinc chloride, 1 part of buffering agent, 1 part of modified additive and the balance of water.

Specifically, the preparation method of the modified additive comprises the following steps:

1) the additive is prepared by using a graphite rod as an electric arc method, wherein the cathode and the anode of 2 graphite rods are oppositely placed in a reaction medium, and high-voltage current of 1.5 kiloamperes is introduced for direct current electric arc discharge to prepare an anode product of the graphite rod, namely the additive.

2) And putting the prepared additive into a constant temperature area of a quartz tube, introducing water, heating to 800 ℃, and applying a voltage of 300V to react for 18h to obtain the modified additive.

Specifically, the manganese dioxide is alpha-MnO₂The nano-sized alpha-MnO 2 material is beneficial to H⁺And Zn₂ ⁺The nano-sized alpha-MnO 2 can reduce the internal resistance of the battery, the buffering agent is ammonium acetate, and the ammonium acetate is weak acid weak base salt and is used for inhibiting H in continuous discharge⁺Reduction to H₂Slow down H₂The gas is generated, the gassing amount of the battery is reduced, the gas expansion of the battery is prevented, the pH change of the whole battery discharging process is controlled, the system is controlled in an acidic range, and Zn (NH) is reduced as much as possible₃)4CL₂Increase the leakage-proof performance, prolong the service life of the battery, and excessive H in continuous discharge⁺Combines with weak acid root of buffer substance to form weak acid difficult to ionize, thereby reducing H generated in continuous discharge reaction⁺The concentration of the hydrogen peroxide enables the pH of a battery system not to be obviously changed, inhibits the reduction of H < + > into H2 and reduces the gassing amount of the battery.

Specifically, the carbon material is one of conductive carbon black, expanded graphite, a carbon nanotube, graphene and carbon fiber.

A manufacturing process of a carbon zinc-manganese dioxide dry battery with high current utilization rate comprises the following steps:

step 1, adding ammonium chloride, zinc chloride and a buffer agent into a stirring container, and fully stirring and mixing to form a pasty mixture;

step 2, adding a carbon material, manganese dioxide powder and a certain mass percent of modified additive into the pasty mixture prepared in the step 1, stirring at a high speed for 1h in a vacuum environment to obtain electrolyte slurry, and aging the obtained electrolyte slurry for more than 24 hours;

and 3, sleeving diaphragm paper on the inner wall of the negative electrode zinc cylinder, injecting aged electrolyte slurry with the filling amount being 1/2-4/5 of the height of the zinc cylinder, inserting a carbon rod as a current collector, coating sealing glue, adding a combined cap, and performing edge rolling and sealing on a machine to obtain the carbon zinc-manganese dry battery.

Example two:

the utility model provides a high utilization rate of electric current carbon nature zinc-manganese dioxide dry battery, includes negative pole zinc can, electrolyte thick liquids, carbon-point, sets up diaphragm and combination cap between compound positive pole and negative pole zinc can, and the electrolyte includes the composition of following parts by weight: 70 parts of manganese dioxide, 9 parts of carbon material, 6 parts of ammonium chloride, 5 parts of zinc chloride, 1.5 parts of buffering agent, 1.5 parts of modified additive and the balance of water.

Specifically, the preparation method of the modified additive comprises the following steps:

1) the additive is prepared by using a graphite rod as an electric arc method, wherein the cathode and the anode of 2 graphite rods are oppositely placed in a reaction medium, and high-voltage current of 1.5 kiloamperes is introduced for direct current electric arc discharge to prepare an anode product of the graphite rod, namely the additive.

2) And putting the prepared additive into a constant temperature area of a quartz tube, introducing water, heating to 1000 ℃, and applying a voltage of 400V to react for 27h to obtain the modified additive.

Specifically, the manganese dioxide is alpha-MnO₂The nano-sized alpha-MnO 2 material is beneficial to H⁺And Zn₂ ⁺The nano-sized alpha-MnO 2 can reduce the internal resistance of the battery, the buffering agent is ammonium acetate, and the ammonium acetate is weak acid weak base salt and is used for inhibiting H in continuous discharge⁺Reduction to H₂Slow down H₂The gas is generated, the gassing amount of the battery is reduced, the gas expansion of the battery is prevented, the pH change of the whole battery discharging process is controlled, the system is controlled in an acidic range, and Zn (NH) is reduced as much as possible₃)4CL₂Increase the leakage-proof performance, prolong the service life of the battery, and excessive H in continuous discharge⁺Combines with weak acid root of buffer substance to form weak acid difficult to ionize, thereby reducing H generated in continuous discharge reaction⁺The concentration of the hydrogen peroxide enables the pH of a battery system not to be obviously changed, inhibits the reduction of H < + > into H2 and reduces the gassing amount of the battery.

Specifically, the carbon material is one of conductive carbon black, expanded graphite, a carbon nanotube, graphene and carbon fiber.

A manufacturing process of a carbon zinc-manganese dioxide dry battery with high current utilization rate comprises the following steps:

step 1, adding ammonium chloride, zinc chloride and a buffer agent into a stirring container, and fully stirring and mixing to form a pasty mixture;

step 2, adding a carbon material, manganese dioxide powder and a certain mass percent of modified additive into the pasty mixture prepared in the step 1, stirring at a high speed for 1.5 hours in a vacuum environment to obtain electrolyte slurry, and aging the obtained electrolyte slurry for more than 24 hours;

and 3, sleeving diaphragm paper on the inner wall of the negative electrode zinc cylinder, injecting aged electrolyte slurry with the filling amount being 1/2-4/5 of the height of the zinc cylinder, inserting a carbon rod as a current collector, coating sealing glue, adding a combined cap, and performing edge rolling and sealing on a machine to obtain the carbon zinc-manganese dry battery.

Example three:

the utility model provides a high utilization rate of electric current carbon nature zinc-manganese dioxide dry battery, includes negative pole zinc section of thick bamboo, electrolyte thick liquids, carbon-point, sets up diaphragm and the combination cap between compound positive pole and negative pole zinc section of thick bamboo, the composition of electrolyte weight parts: 80 parts of manganese dioxide, 10 parts of carbon material, 7 parts of ammonium chloride, 6 parts of zinc chloride, 2 parts of buffering agent, 2 parts of modified additive and the balance of water.

Specifically, the preparation method of the modified additive comprises the following steps:

1) the additive is prepared by using a graphite rod as an electric arc method, wherein the cathode and the anode of 2 graphite rods are oppositely placed in a reaction medium, and high-voltage current of 1.5 kiloamperes is introduced for direct current electric arc discharge to prepare an anode product of the graphite rod, namely the additive.

2) And putting the prepared additive into a constant temperature area of a quartz tube, introducing water, heating to 1200 ℃, and applying a voltage of 500V to react for 36h to obtain the modified additive.

Specifically, the manganese dioxide is alpha-MnO₂The nano-sized alpha-MnO 2 material is beneficial to H⁺And Zn₂ ⁺The nano-sized alpha-MnO 2 can reduce the internal resistance of the battery, the buffering agent is ammonium acetate, and the ammonium acetate is weak acid weak base salt and is used for inhibiting H in continuous discharge⁺Reduction to H₂Slow down H₂The gas is generated, the gassing amount of the battery is reduced, the gas expansion of the battery is prevented, the pH change of the whole battery discharging process is controlled, the system is controlled in an acidic range, and Zn (NH) is reduced as much as possible₃)4CL₂Increase the leakage-proof performance, prolong the service life of the battery, and excessive H in continuous discharge⁺Combines with weak acid root of buffer substance to form weak acid difficult to ionize, thereby reducing H generated in continuous discharge reaction⁺The concentration of the hydrogen peroxide enables the pH of a battery system not to be obviously changed, inhibits the reduction of H < + > into H2 and reduces the gassing amount of the battery.

Specifically, the carbon material is one of conductive carbon black, expanded graphite, a carbon nanotube, graphene and carbon fiber.

A manufacturing process of a carbon zinc-manganese dioxide dry battery with high current utilization rate comprises the following steps:

step 1, adding ammonium chloride, zinc chloride and a buffer agent into a stirring container, and fully stirring and mixing to form a pasty mixture;

step 2, adding a carbon material, manganese dioxide powder and a certain mass percent of modified additive into the pasty mixture prepared in the step 1, stirring at a high speed for 2 hours in a vacuum environment to obtain electrolyte slurry, and aging the obtained electrolyte slurry for more than 24 hours;

and 3, sleeving diaphragm paper on the inner wall of the negative electrode zinc cylinder, injecting aged electrolyte slurry with the filling amount being 1/2-4/5 of the height of the zinc cylinder, inserting a carbon rod as a current collector, coating sealing glue, adding a combined cap, and performing edge rolling and sealing on a machine to obtain the carbon zinc-manganese dry battery.

The foregoing is only a preferred embodiment of the present invention; the scope of the invention is not limited thereto. Any person skilled in the art should be able to cover the technical scope of the present invention by equivalent or modified solutions and modifications within the technical scope of the present invention.