CN105932312B - Carbon battery with low gas evolution amount and preparation method thereof - Google Patents

Carbon battery with low gas evolution amount and preparation method thereof Download PDF

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CN105932312B
CN105932312B CN201610319726.0A CN201610319726A CN105932312B CN 105932312 B CN105932312 B CN 105932312B CN 201610319726 A CN201610319726 A CN 201610319726A CN 105932312 B CN105932312 B CN 105932312B
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battery
electrolyte
weak acid
positive electrode
material mixture
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CN105932312A (en
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刘建纯
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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
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/04—Cells with aqueous electrolyte
    • H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
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Abstract

The invention relates to a carbon battery with low gas evolution quantity, which comprises: a positive electrode material mixture containing manganese dioxide, a negative electrode can containing zinc, a separator disposed between the positive electrode material mixture and the negative electrode can, and an electrolyte,the electrolyte contains weak acid, weak base and salt as buffering agent. The invention adds weak acid and weak base salt as buffer agent into electrolyte for inhibiting H in continuous discharge+Reduction to H2Slow down H2The gas is generated, so that the gassing amount of the battery is reduced, and the gas expansion of the battery is prevented; the pH change of the whole battery discharge process is controlled, the system is controlled in an acidic range, and Zn (NH) is reduced as much as possible3)4CL2Generation of (2), inhibition of H+Reduction to H2The leakage-proof performance is improved, and the service life of the battery is prolonged. Adding weak acid weak base salt, 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+Concentration, no obvious change of pH value of battery system, and inhibition of H+Reduction to H2The amount of (c) reduces the gassing volume of the battery.

Description

Carbon battery with low gas evolution amount and preparation method thereof
Technical Field
The invention relates to a carbon battery, in particular to a carbon battery with low gas evolution and a preparation method 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. Since the electrolyte of such a chemical power supply device is an immobile pulp paste, it is also called a dry cell, as opposed to a cell with a flowable electrolyte. The service life and storage life of carbon batteries are largely material-related qualities, but more importantly the preference of the formulation. The carbon battery with good comprehensive performance, such as good battery storage performance, small gas evolution amount and the like, particularly in the aspect of controlling the gas evolution amount, gas generated in the battery is reduced by various ways for various battery production enterprises, the carbon battery discharges with large current in the discharging process, and H is+Continuously increased while being reduced to H2So that H of the battery system+The ion concentration decreases, which means that the pH in the system increases, and the pH increases to Zn (NH) which is hardly soluble, particularly at 24 hours, since the pH increases in the late stage of 3.9 Ω continuous discharge of the ammonium type battery3)2CL2Conversion to soluble Zn (NH) with fluidity3)4CL2And a large amount of gas is generated. At present, methods such as adding metal oxide into the positive electrode material are commonly adopted, however, the improvement of the battery performance is limited to a certain extent because of the limitation of the raw material process and the relative influence of the metal oxide on the battery performance, and the gas evolution quantity of the battery in the storage and use processes is not controlled.
Disclosure of Invention
The invention provides a carbon battery with low gas evolution amount and a preparation method thereof, which aim to solve the technical problems.
In order to achieve the purpose, the technical scheme of the invention is realized as follows: a low gassing carbon battery comprising: the electrolyte includes a positive electrode material mixture containing manganese dioxide, a negative electrode can containing zinc, a separator disposed between the positive electrode material mixture and the negative electrode can, and an electrolyte containing a weak acid and weak base salt as a buffer.
Further, the buffer is ammonium acetate.
Further, the electrolyte comprises the following components in percentage by weight: 15 to 25 weight percent of ammonium chloride, 10 to 15 weight percent of zinc chloride and 0.8 to 1.5 weight percent of ammonium acetate.
Further, the electrolyte comprises the following components in percentage by weight: 15 to 25 weight percent of ammonium chloride, 10 to 15 weight percent of zinc chloride and 0.8 to 1.2 weight percent of ammonium acetate.
Further, the electrolyte comprises the following components in percentage by weight: 15-25 wt% of ammonium chloride, 10-15 wt% of zinc chloride and 1 wt% of ammonium acetate.
A method for preparing any one of the low gas evolution carbon batteries comprises the following steps: after a buffer is mixed in the positive electrode material mixture and the positive electrode material mixture, the negative electrode can, the separator, and the electrolyte are assembled into the carbon battery, the buffer permeates from the positive electrode material mixture to the separator.
Compared with the prior art, the invention has the advantages that: according to the invention, a buffering principle is introduced into the electrolyte, and weak acid and weak base salts are added to inhibit H + from being reduced into H2 in continuous discharge, so that the generation of H2 gas is slowed down, the gassing amount of the battery is reduced, and the gas expansion of the battery is prevented; the pH change of the whole battery discharge process is controlled, the system is controlled in an acidic range, the generation of Zn (NH3)4CL2 is reduced as much as possible, the leakage-proof performance is improved, and the service life of the battery is prolonged. And (2) adding weak acid weak base salt, wherein excessive H & lt + & gt is combined with weak acid radicals of buffer substances to synthesize weak acid difficult to ionize during continuous discharging, so that the concentration of H & lt + & gt generated in the continuous discharging reaction is reduced, the pH of a battery system is not obviously changed, the reduction of H & lt + & gt to H2 is inhibited, and the gas evolution rate of the battery is reduced.
Detailed Description
The technical solutions of the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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 present invention is described in further detail below with reference to specific examples.
Example 1
Embodiment 1 of the present invention relates to a carbon battery with a low gas evolution amount, including: the electrolyte includes a positive electrode material mixture containing manganese dioxide, a negative electrode can containing zinc, a separator disposed between the positive electrode material mixture and the negative electrode can, and an electrolyte containing a weak acid and weak base salt as a buffer.
The invention introduces a buffer principle into the electrolyte, adds weak acid and weak base salt for inhibiting H in continuous discharge+Reduction to H2Slow down H2The gas is generated, so that the gassing amount of the battery is reduced, and the gas expansion of the battery is prevented; the pH change of the whole battery discharge process is controlled, the system is controlled in an acidic range, and Zn (NH) is reduced as much as possible3)4CL2The leakage-proof performance is improved, and the service life of the battery is prolonged. Adding weak acid weak base salt, 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+Concentration, no obvious change of pH value of battery system, and inhibition of H+Reduction to H2The amount of (c) reduces the gassing volume of the battery.
Preferably, the buffer is ammonium acetate.
The ammonium acetate is a neutral substance, and is added into the electrolyte, so that the original acidity of the electrolyte is not obviously changed; the ammonium acetate and the ammonium chloride of the battery belong to the same ion effect, so that no mutual influence exists; it is possible to provide NH4+Participate in the discharge reaction of the battery, help to improve the discharge performance; ammonium acetate is a strong electrolyte and has negligible effect on the internal resistance of the battery when added into the battery system. When continuously discharging, H+Increase, too much H+With CH3COO of a buffer substance-Combines with CH3COOH which is difficult to ionize, so that the buffer balance is moved leftwards, thereby reducing H generated in the continuous amplification reaction+Concentration, inhibition of H+Reduction ofIs H2Amount of (1), slow down H2The gas is generated, so that the gassing amount of the battery is reduced, and the gas expansion of the battery is prevented; the pH change of the whole battery discharge process is controlled, the system is controlled in an acidic range, and Zn (NH) is reduced as much as possible3)4CL2The leakage-proof performance is improved, and the service life of the battery is prolonged.
Preferably, the electrolyte comprises the following components in percentage by weight: 15 to 25 weight percent of ammonium chloride, 10 to 15 weight percent of zinc chloride and 0.8 to 1.5 weight percent of ammonium acetate.
A method of making the low gassing carbon cell of this example: after a buffer is mixed in the positive electrode material mixture and the positive electrode material mixture, the negative electrode can, the separator, and the electrolyte are assembled into the carbon battery, the buffer permeates from the positive electrode material mixture to the separator.
Example 2
Embodiment 2 of the present invention relates to a carbon battery with a low gas evolution amount, including: the electrolyte includes a positive electrode material mixture containing manganese dioxide, a negative electrode can containing zinc, a separator disposed between the positive electrode material mixture and the negative electrode can, and an electrolyte containing a weak acid and weak base salt as a buffer.
The invention introduces a buffer principle into the electrolyte, adds weak acid and weak base salt for inhibiting H in continuous discharge+Reduction to H2Slow down H2The gas is generated, so that the gassing amount of the battery is reduced, and the gas expansion of the battery is prevented; the pH change of the whole battery discharge process is controlled, the system is controlled in an acidic range, and Zn (NH) is reduced as much as possible3)4CL2The leakage-proof performance is improved, and the service life of the battery is prolonged. Adding weak acid weak base salt, 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+Concentration, no obvious change of pH value of battery system, and inhibition of H+Reduction to H2The amount of (c) reduces the gassing volume of the battery.
Preferably, the buffer is ammonium acetate.
Ammonium acetate is neutral substance, and is added into electrolyte to make electrolyte possess original acidThe degree is not obviously changed; the ammonium acetate and the ammonium chloride of the battery belong to the same ion effect, so that no mutual influence exists; it is possible to provide NH4+Participate in the discharge reaction of the battery, help to improve the discharge performance; ammonium acetate is a strong electrolyte and has negligible effect on the internal resistance of the battery when added into the battery system. When continuously discharging, H+Increase, too much H+Combines with CH3 COO-of the buffer substance to form difficult-to-ionize CH3COOH, so that the buffer balance is moved leftwards, thereby reducing H generated in the continuous discharge reaction+Concentration, inhibition of H+Reduction to H2Amount of (1), slow down H2The gas is generated, so that the gassing amount of the battery is reduced, and the gas expansion of the battery is prevented; the pH change of the whole battery discharge process is controlled, the system is controlled in an acidic range, and Zn (NH) is reduced as much as possible3)4CL2The leakage-proof performance is improved, and the service life of the battery is prolonged.
Preferably, the electrolyte comprises the following components in percentage by weight: 15 to 25 weight percent of ammonium chloride, 10 to 15 weight percent of zinc chloride and 0.8 to 1.2 weight percent of ammonium acetate.
A method of making the low gassing carbon cell of this example: after a buffer is mixed in the positive electrode material mixture and the positive electrode material mixture, the negative electrode can, the separator, and the electrolyte are assembled into the carbon battery, the buffer permeates from the positive electrode material mixture to the separator.
Example 3
Embodiment 3 of the present invention relates to a carbon battery having a low gas evolution amount, including: the electrolyte includes a positive electrode material mixture containing manganese dioxide, a negative electrode can containing zinc, a separator disposed between the positive electrode material mixture and the negative electrode can, and an electrolyte containing a weak acid and weak base salt as a buffer.
The invention introduces a buffer principle into the electrolyte, adds weak acid and weak base salt for inhibiting H in continuous discharge+Reduction to H2Slow down H2The gas is generated, so that the gassing amount of the battery is reduced, and the gas expansion of the battery is prevented; the pH change of the whole battery discharge process is controlled, the system is controlled in an acidic range, and Zn (NH) is reduced as much as possible3)4CL2To improve leakage preventionPerformance, and battery life. Adding weak acid weak base salt, 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+Concentration, no obvious change of pH value of battery system, and inhibition of H+Reduction to H2The amount of (c) reduces the gassing volume of the battery.
Preferably, the buffer is ammonium acetate.
The ammonium acetate is a neutral substance, and is added into the electrolyte, so that the original acidity of the electrolyte is not obviously changed; the ammonium acetate and the ammonium chloride of the battery belong to the same ion effect, so that no mutual influence exists; it is possible to provide NH4+Participate in the discharge reaction of the battery, help to improve the discharge performance; ammonium acetate is a strong electrolyte and has negligible effect on the internal resistance of the battery when added into the battery system. When continuously discharging, H+Increase, too much H+With CH3COO of a buffer substance-Combines with CH3COOH which is difficult to ionize, so that the buffer balance is moved leftwards, thereby reducing H generated in the continuous amplification reaction+Concentration, inhibition of H+Reduction to H2Amount of (1), slow down H2The gas is generated, so that the gassing amount of the battery is reduced, and the gas expansion of the battery is prevented; the pH change of the whole battery discharge process is controlled, the system is controlled in an acidic range, and Zn (NH) is reduced as much as possible3)4CL2The leakage-proof performance is improved, and the service life of the battery is prolonged.
Preferably, the electrolyte comprises the following components in percentage by weight: 15-25 wt% of ammonium chloride, 10-15 wt% of zinc chloride and 1 wt% of ammonium acetate.
A method of making the low gassing carbon cell of this example: after a buffer is mixed in the positive electrode material mixture and the positive electrode material mixture, the negative electrode can, the separator, and the electrolyte are assembled into the carbon battery, the buffer permeates from the positive electrode material mixture to the separator.
The low gassing amount carbon batteries according to embodiments 1 to 3 of the present invention have lower gassing amount and better electrical properties than the existing carbon batteries in which metal oxide is added to the positive electrode and ammonium acetate is added to other contents.
The specific data are shown in table one and table two.
Table 1: comparison of voltage and generated gas amount of battery with different weight percentages of ammonium acetate buffer and metal oxide battery
As is clear from the above expression 1, the content of silica gel in fresh electric power, voltage at room temperature and constant temperature is not preferred as the content of ammonium acetate is larger but is more preferred as the content of ammonium acetate is 1.0% by weight.
Table 2: the discharge performance (3.9 omega continuous discharge) of the battery added with ammonium acetate with different weight percentages is compared with that of the battery added with metal oxide as the anode, and the electric performance and the storage performance of the battery are mainly verified
As can be seen from the results of Table 2, the discharge at the fresh state, the normal temperature and the constant temperature is the performance, and it is not preferable that the weight percentage of ammonium acetate is larger but is most preferable that the weight percentage of ammonium acetate is added to be 1.0 wt%.
The above description is only a preferred embodiment of the present invention, and should not be taken as limiting the invention in any way, and any person skilled in the art can make many changes or modifications to the equivalent embodiments without departing from the scope of the present invention.

Claims (2)

1. A low gassing carbon battery comprising: a positive electrode material mixture comprising manganese dioxide, a negative electrode can comprising zinc, a separator disposed between the positive electrode material mixture and the negative electrode can, and an electrolyte comprising a weak acid, weak base salt as a buffer; the buffer is ammonium acetate; the electrolyte comprises the following components in percentage by weight: 15-25 wt% of ammonium chloride, 10-15 wt% of zinc chloride and 1 wt% of ammonium acetate.
2. A method for producing a low gassing amount carbon battery as defined in claim 1, characterized in that: the buffer agent is mixed in the positive electrode material mixture, and after the positive electrode material mixture, the negative electrode case, the separator, and the electrolyte are assembled into the carbon battery, the buffer agent permeates from the positive electrode material mixture to the separator.
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CN101828284A (en) * 2008-08-29 2010-09-08 松下电器产业株式会社 Manganese dry battery
WO2016014554A1 (en) * 2014-07-21 2016-01-28 Flexel, Llc Flexible micro-battery

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WO2011112992A1 (en) * 2010-03-12 2011-09-15 Energ2, Inc. Mesoporous carbon materials comprising bifunctional catalysts
US20120021303A1 (en) * 2010-07-21 2012-01-26 Steven Amendola Electrically rechargeable, metal-air battery systems and methods

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Publication number Priority date Publication date Assignee Title
CN101828284A (en) * 2008-08-29 2010-09-08 松下电器产业株式会社 Manganese dry battery
WO2016014554A1 (en) * 2014-07-21 2016-01-28 Flexel, Llc Flexible micro-battery

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