CN113937280A - Zinc paste gel, method for preparing zinc paste by using zinc paste gel and zinc paste prepared by using zinc paste gel - Google Patents

Zinc paste gel, method for preparing zinc paste by using zinc paste gel and zinc paste prepared by using zinc paste gel Download PDF

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CN113937280A
CN113937280A CN202111010912.3A CN202111010912A CN113937280A CN 113937280 A CN113937280 A CN 113937280A CN 202111010912 A CN202111010912 A CN 202111010912A CN 113937280 A CN113937280 A CN 113937280A
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zinc powder
zinc
bpei
calamine cream
paa
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CN113937280B (en
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李海东
陈超
程凤梅
吴吉娜
陈洪旭
谢解解
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Zhejiang Hengwei Battery Ltd By Share Ltd
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Zhejiang Hengwei Battery Ltd By Share Ltd
Jiaxing University
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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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • 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
    • H01M4/57—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead of "grey lead", i.e. powders containing lead and lead oxide
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0893—Zinc
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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

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Abstract

The invention relates to a calamine cream gelata, a method for preparing calamine cream by using the calamine cream gelata and calamine cream prepared by using the calamine cream gelata, wherein the calamine cream gelata comprises a main substance (PAA and/or PAAS) and an auxiliary substance (BPEI); the method for preparing the zinc paste comprises the following steps: firstly, adding a main substance into an electrolyte, uniformly stirring, then adding an auxiliary substance, uniformly stirring to obtain a mixed solution, finally adding a corrosion inhibitor and zinc powder, heating and uniformly stirring to obtain a zinc paste; in the prepared zinc paste, zinc powder is uniformly dispersed and is combined with amino on an auxiliary substance branched chain through a hydrogen bond; the carboxyl on the main chain of the main substance and the amino on the branched chain of the auxiliary substance generate ionic bond crosslinking and covalent bond crosslinking to form a three-dimensional network structure with branched chains. The invention forms three-dimensional network type composite gel by crosslinking PAA or PAAS and BPEI, solves the problems of limited contact with zinc particles and poor storage stability, and improves the suspension property, the conductivity and the water retention property of zinc powder.

Description

Zinc paste gel, method for preparing zinc paste by using zinc paste gel and zinc paste prepared by using zinc paste gel
Technical Field
The invention belongs to the technical field of alkaline zinc-manganese batteries, and relates to a zinc cream gel, a method for preparing zinc cream by using the zinc cream gel, and the zinc cream prepared by using the zinc cream gel.
Background
Alkaline zinc manganese batteries are the most widely used commercial battery products to date. The zinc paste is used as an important component material for preparing the alkaline zinc-manganese battery, and the performance of the zinc paste plays a key role in the discharge capacity and the service life of the alkaline battery.
The calamine cream gelata is one of key materials for preparing cathode calamine cream in an alkaline manganese battery, can play multiple roles, and can uniformly disperse zinc powder during the cream activation and fix the zinc powder without swaying after being injected into a battery shell; the electrolyte can be absorbed and fixed by the surface body, and sufficient electrolyte is provided for the reaction of the zinc cathode; the surface is present to prevent the solid-liquid separation of the battery during storage; and on the other hand, the surface performance of the zinc powder can be improved, and the discharge performance of the battery can be improved.
At present, battery enterprises generally use PAA (polyacrylic acid) and PAAS (sodium polyacrylate) as zinc paste gels, which have good initial stability and high viscosity in strong alkaline solution, so that zinc powder has good suspension stability, but the prior art is difficult to prepare batteries with small internal resistance, excellent discharge performance and excellent storage performance by using the zinc paste gels, and the reasons for this are that: in the early stage of preparation (namely, in the wet paste activating process), because the viscosity of PAA or PAAS is high, the zinc powder is difficult to be uniformly dispersed in the solution of PAA or PAAS, and further, the zinc paste in which the zinc powder is uniformly dispersed is difficult to be obtained; in the later stage of preparation, because PAA or PAAS is a linear polymer and is limited by a one-dimensional linear structure, and the contact with zero-dimensional zinc particles is limited to point-line contact, the contact area is limited, and zinc powder cannot be further uniformly dispersed in the process of preparing the zinc paste; in the storage process, because zinc powder in the zinc paste can not stably suspend for a long time, the zinc powder can be settled and agglomerated after long-time use, in addition, PAA or PAAS can be gradually decomposed under a strong alkaline condition in the long-term storage process, the zinc powder can not be effectively adsorbed at the limited sites of the PAA or PAAS linear structure, a three-dimensional network structure can not be formed to limit the displacement of the zinc powder, and finally, the zinc powder can be separated from pulp in the long-term storage process, so that the zinc powder is settled and agglomerated, and the discharge performance of the battery is reduced.
Therefore, a new calamine cream gel is needed to be researched to prepare a battery with small internal resistance, excellent discharge performance and excellent storage performance.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a calamine cream gel, a method for preparing calamine cream by using the calamine cream gel and the calamine cream prepared by using the calamine cream gel.
In order to achieve the purpose, the invention adopts the following scheme:
a calamine cream gel comprises main material and auxiliary material; the main substance is PAA and/or PAAS; the auxiliary substance is BPEI (hyperbranched polyethyleneimine); compared with a one-dimensional linear structure polymer, the hyperbranched polymer contains a large number of branched chains with topological structures, the branched chains can increase the contact area of the branched chains and zinc powder, and a new structure formed by PAA and/or PAAS and BPEI has a rigid 'frame' formed by the PAA and/or PAAS and a 'whisker' formed by a large number of branched chains rich in amino groups of BPEI, wherein the 'frame' is helpful for limiting the space displacement of the zinc powder, and the 'whisker' can provide a large number of sites for firmly adsorbing the zinc powder, so that the suspension performance of the zinc powder is obviously improved.
As a preferred technical scheme:
the weight average molecular weight of the BPEI is 45000-75000 g/mol; if the molecular weight is too low, the viscosity is low, the number of branched chains is small, and the suspension and the adsorption of zinc powder are not facilitated; if the molecular weight is too large, the polymer is easy to agglomerate and is difficult to form a uniformly crosslinked three-dimensional network structure.
The mass ratio of the main substance to the auxiliary substance of the calamine cream gel is 97 to 60; when the content of the BPEI is less than 3 percent, the BPEI cannot be crosslinked with the PAA or the PAAS to form a three-dimensional network; the BPEI content is higher than 40%, and the viscosity of the BPEI is lower than that of PAA, so that the viscosity of the whole gel is greatly reduced due to excessive addition of the BPEI, and the suspension of zinc powder is not facilitated.
The invention also provides a method for preparing the calamine cream by adopting the calamine cream gel, which comprises the steps of firstly adding the main substances into the electrolyte, uniformly stirring, then adding the auxiliary substances, uniformly stirring to obtain a mixed solution, finally adding the corrosion inhibitor and the zinc powder, heating to 70-90 ℃, and uniformly stirring to obtain the calamine cream.
As a preferred technical scheme:
in the above method, the electrolyte is a KOH solution; the corrosion inhibitor is indium hydroxide.
In the method, the apparent weight ratio of the zinc powder is 2-4 g/mL.
The method is characterized in that the concentration of the electrolyte is 20-45 wt%; the total content of the main substances and the auxiliary substances in the mixed solution is 1 to 10 weight percent; the mass ratio of the zinc powder to the mixed solution is 1.5-2.5; the mass ratio of the corrosion inhibitor to the zinc powder is 0.05.
The invention also provides the zinc paste prepared by the method, which comprises the main substance, the auxiliary substance, electrolyte, corrosion inhibitor and zinc powder; the zinc powder is uniformly dispersed and is combined with the amino on the auxiliary substance branched chain through a hydrogen bond; the carboxyl on the main material main chain and the amino on the auxiliary material branched chain generate ionic bond crosslinking and covalent bond crosslinking to form a three-dimensional network structure with a plurality of branched chains.
As a preferred technical scheme:
the calamine cream is characterized in that the internal resistance of an LR6 battery made of the calamine cream is 49-78 omega, the discharge frequency is 129-174 times, and the discharge performance reduction rate after storage is 10.2-18.7%.
The principle of the invention is as follows:
the invention aims to research a novel calamine cream gel to prepare a battery with small internal resistance, excellent discharge performance and excellent storage performance; the main substance is PAA and/or PAAS; the auxiliary substance is BPEI (hyperbranched polyethyleneimine).
Compared with a one-dimensional linear structure polymer, the hyperbranched polymer contains a large number of branched chains with topological structures, and the branched chains can increase the contact area of the branched chains and zinc powder and are beneficial to uniformly dispersing the zinc powder; therefore, the problems that the contact area is limited and the zinc powder cannot be further uniformly dispersed in the process of preparing the zinc paste because the PAA or PAAS is a linear polymer and is limited by a one-dimensional linear structure and the contact with the zero-dimensional zinc particles is limited by point-line contact are solved, and the discharge performance of the battery is favorably improved;
the BPEI branched chain contains a large amount of amino groups, has more contact sites with zinc powder, and can form hydrogen bonds with an oxide layer on the surface of the zinc powder to firmly adsorb the zinc powder; the PAA or PAAS and the BPEI can be crosslinked through ionic bonds and covalent bonds, so that the zinc paste forms a stable three-dimensional network structure, and the BPEI can firmly adsorb zinc powder particles, so that the zinc powder is uniformly dispersed and stably suspended and is not easy to settle and agglomerate; the novel structure formed by PAA or PAAS and BPEI has a rigid 'frame' formed by PAA or PAAS and a 'whisker' formed by BPEI a large number of branched chains rich in amino groups, wherein the 'frame' is helpful for limiting the space displacement of zinc powder, and the 'whisker' can provide a large number of sites for firmly adsorbing the zinc powder and remarkably improve the suspension performance of the zinc powder; therefore, the problems that zinc powder in the zinc paste prepared by adopting PAA or PAAS as the zinc paste gel can not stably suspend and can be settled and agglomerated after long-time use are solved, and the discharge performance of the battery is favorably improved;
according to the invention, the BPEI is used as an auxiliary substance of the zinc cream gel, a large number of amino groups on a BPEI hyperbranched chain can be complexed with zinc ions, so that the quantity and speed of zinc hydroxide and other zinc oxides generated by the reaction of the zinc ions and hydroxyl in electrolyte are reduced and slowed down, the generation of a compact oxide layer on the surface of zinc particles is reduced, the surface resistance of the zinc particles is reduced, and the discharge performance of the zinc cream gel is improved; therefore, the problems that the anode active material of the zinc-manganese alkaline battery is zinc powder, the alkaline aqueous solution is used as electrolyte, and the zinc hydroxide, the zinc oxide and the like generated by the discharge reaction can form a compact oxide layer on the surface of the zinc powder, so that passivation is caused, the internal resistance is increased, and the discharge performance of the zinc-manganese alkaline battery is reduced are solved, and the discharge performance of the battery is improved;
the BPEI is used as an auxiliary substance of the zinc paste gel, on one hand, the BPEI is a hyperbranched three-dimensional topological structure, so that a large number of contact sites with zinc particles are provided for the zinc paste gel, and in addition, a large number of amino functional groups on branched chains of the BPEI can form hydrogen bonds with an oxide layer on the surface of zinc; on the other hand, the amino group on the BPEI is also an excellent hydrophilic group, and the BPEI has excellent water retention and water locking performances by matching with a hyperbranched structure of the BPEI, so that the storage performance of the BPEI is improved;
in addition, in the process of preparing the zinc paste, PAA or PAAS and BPEI can be crosslinked through ionic bonds and covalent bonds, so that the zinc paste forms a stable three-dimensional network structure, and the formation of the three-dimensional network is also beneficial to improving the suspension property, the water retention property and the water locking property of the zinc powder, thereby improving the storage property of the zinc powder; therefore, the problems that the PAA or PAAS can be gradually decomposed under a strong alkali condition in the long-term storage process, the limited sites of the PAA or PAAS linear structure can not effectively adsorb zinc powder, a three-dimensional network structure can not be formed to limit the displacement of the zinc powder, and finally the separation of slurry can be generated in the long-term storage process, so that the zinc powder sinks and is agglomerated, and the discharge performance of the battery is reduced are solved, and the storage performance of the battery is favorably improved.
Advantageous effects
(1) The preparation method of the ionic bond self-crosslinking gelata applied to the calamine cream in the alkaline zinc-manganese dioxide battery is different from linear polymer gelata materials such as PAA or PAAS, the auxiliary component of the calamine cream gelata in the invention is BPEI which is a hyperbranched polymer structure, and the branched chain of the calamine cream gelata contains rich amino functional groups capable of firmly adsorbing zinc powder, thereby improving the suspension property of the zinc powder;
(2) The preparation method of the ionic bond self-crosslinking gel applied to the calamine cream in the alkaline zinc-manganese battery of the invention, cross-link PAA or PAAS and BPEI to form the three-dimensional network type compound gel through ionic bond and covalent bond, do not need to carry on the chemical modification to PAA, PAAS, needn't synthesize PAA, PAAS with special structure even more, therefore simple and easy; the problem that the BPEI is easy to agglomerate when used alone can be effectively prevented, so that the BPEI is uniformly dispersed in a network, the function of the BPEI as a gel component is better exerted, and the problems that the linear polymer materials PAA and PAAS are limited in contact with zinc particles and poor in long-term storage stability when used alone are also effectively solved;
(3) Compared with the single use of the PAA, the PAAS or the BPEI, and the compounding of the PAA or the PAAS and the BPEI, the synergistic effect on the structure and the function ensures that the suspension property, the electrical conductivity and the water retention and water locking performance of the zinc powder are greatly improved.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention can be made by those skilled in the art after reading the teaching of the present invention, and these equivalents also fall within the scope of the claims appended to the present application.
Some performance indicators in the following examples and comparative examples were tested as follows:
zinc powder settling rate: weighing 5g of a vacuum-dried calamine cream sample, slowly adding the calamine cream sample into 100g of KOH solution with the concentration of 40wt%, stirring for 1h, finally removing mixed bubbles under reduced pressure to obtain a zinc powder suspension, putting the zinc powder suspension into a 5mL centrifuge tube, shaking and falling the zinc powder suspension on a tap density instrument at the frequency of 300 times/min to accelerate the sedimentation of the zinc powder, and evaluating the suspension performance of the zinc powder according to the height of the zinc powder in the centrifuge tube (namely the height difference of the zinc powder in the suspension before and after shaking and falling), wherein the calculation formula of the sedimentation rate of the zinc powder is as follows:
zinc powder settling rate = (height of zinc powder settling/total height of zinc powder suspension) × 100%.
Battery internal resistance: and testing by using a battery internal resistance tester.
The number of discharges: the batteries are respectively subjected to high-power discharge of 500mw 2s,650mw 28s, 10 times per hour, 24 hours per day and cutoff voltage of 1.05V for 5 times by adopting a primary battery performance tester, and the average value of the discharge times is recorded and calculated.
Rate of decrease in discharge performance after storage: the discharge frequency (i.e., the number of discharges before storage) of the battery was measured by the above method, and then the discharge frequency (i.e., the number of discharges after storage) of the battery was measured by the above method after the battery was stored at 70 ℃ for 7 days (in order to simulate the storage of the battery for 1 to 3 years), and the rate of decrease in discharge performance after storage = (the number of discharges before storage-the number of discharges after storage)/the number of discharges before storage × 100%.
The weight average molecular weight of PAA used in the examples was 450000g/mol, and the weight average molecular weight of PAAS was 450000g/mol.
Example 1
A preparation method of a zinc paste comprises the following specific steps:
at room temperature, firstly adding PAA into KOH solution with the concentration of 20wt% and uniformly stirring, then adding BPEI with the weight-average molecular weight of 60000g/mol and uniformly stirring to obtain mixed solution; finally, adding indium hydroxide and zinc powder with the apparent weight ratio of 2g/mL, heating to 70 ℃, and uniformly stirring to obtain zinc paste; wherein, the total content of PAA and BPEI in the mixed solution is 5wt%; the mass ratio of the PAA to the BPEI is 97; the mass ratio of the zinc powder to the mixed solution is 1.5; the mass ratio of the indium hydroxide to the zinc powder is 0.05.
The prepared zinc paste comprises PAA, BPEI, KOH solution, indium hydroxide and zinc powder; the zinc powder is uniformly dispersed, the sedimentation rate is 6.8%, and the zinc powder is combined with amino on a BPEI branched chain through a hydrogen bond; the carboxyl on the PAA main chain and the amino on the BPEI branched chain generate ionic bond crosslinking and covalent bond crosslinking to form a three-dimensional network structure with a plurality of branched chains.
The LR6 battery made of calamine cream had an internal resistance of 75 Ω, discharge frequency of 130 times, and a discharge performance decrease rate after storage of 16%.
Comparative example 1
A process for preparing a calamine cream, substantially as in example 1, except that BPEI is not added during the preparation.
The prepared calamine cream comprises PAA, KOH solution, indium hydroxide and zinc powder; the zinc powder has poor dispersibility and the sedimentation rate is 8.4 percent.
The LR6 battery made of calamine cream had an internal resistance of 82 Ω, a number of discharges of 123 times, and a rate of decrease in discharge performance after storage was 20.4%.
Compared with example 1, the zinc powder dispersibility and suspension performance of the zinc paste of comparative example 1 are poorer than those of example 1, and the reduction rate of discharge frequency and discharge performance after storage of the prepared battery is inferior to that of example 1, because carboxyl on the PAA main chain and amino on the BPEI branched chain generate ionic bond crosslinking and covalent bond crosslinking to form a three-dimensional network structure with a large number of branched chains in example 1, wherein the three-dimensional network structure 'frame' is helpful for limiting the space displacement of the zinc powder, a large number of branched chains 'tentacles' can provide a large number of sites for firmly adsorbing the zinc powder, and finally, the dispersibility and suspension performance of the zinc powder are remarkably improved.
Example 2
A method of preparing a calamine cream, substantially as in example 1, except that the mass ratio of PAA to BPEI is 90.
The prepared zinc paste comprises PAA, BPEI, KOH solution, indium hydroxide and zinc powder; the zinc powder is uniformly dispersed without obvious sinking and is combined with amino on a BPEI branched chain through a hydrogen bond; carboxyl on the PAA main chain and amino on the BPEI branched chain generate ionic bond crosslinking and covalent bond crosslinking to form a three-dimensional network structure with a plurality of branched chains.
The LR6 battery made of the calamine cream had an internal resistance of 68 Ω, a discharge frequency of 141 times, and a discharge performance decrease rate after storage of 11.4%.
Example 3
A method of preparing a zinc paste, substantially as in example 1, except that the mass ratio of PAA to BPEI is 80.
The prepared zinc paste comprises PAA, BPEI, KOH solution, indium hydroxide and zinc powder; the zinc powder is uniformly dispersed without obvious sedimentation and is combined with amino on a BPEI branched chain through a hydrogen bond; carboxyl on the PAA main chain and amino on the BPEI branched chain generate ionic bond crosslinking and covalent bond crosslinking to form a three-dimensional network structure with a plurality of branched chains.
The LR6 battery made of the calamine cream had an internal resistance of 62 Ω, a discharge frequency of 157 times, and a discharge performance decrease rate after storage of 10.2%.
Example 4
A process for preparing a calamine cream, which is substantially the same as example 1 except that the mass ratio of PAA to BPEI is 70.
The prepared zinc paste comprises PAA, BPEI, KOH solution, indium hydroxide and zinc powder; the zinc powder is uniformly dispersed, the sedimentation rate is 4.9 percent, and the zinc powder is combined with amino on a BPEI branched chain through a hydrogen bond; carboxyl on the PAA main chain and amino on the BPEI branched chain generate ionic bond crosslinking and covalent bond crosslinking to form a three-dimensional network structure with a plurality of branched chains.
The LR6 battery made of calamine cream had an internal resistance of 56 Ω, discharge frequency of 169 times, and a rate of decrease in discharge performance after storage was 13.7%.
Example 5
A method of preparing a zinc paste, substantially as in example 1, except that the mass ratio of PAA to BPEI is 60.
The prepared zinc paste comprises PAA, BPEI, KOH solution, indium hydroxide and zinc powder; the zinc powder is uniformly dispersed, the sedimentation rate is 5.4%, and the zinc powder is combined with amino on a BPEI branched chain through a hydrogen bond; carboxyl on the PAA main chain and amino on the BPEI branched chain generate ionic bond crosslinking and covalent bond crosslinking to form a three-dimensional network structure with a plurality of branched chains.
The LR6 battery made of the calamine cream had an internal resistance of 49 Ω, a discharge frequency of 174 times, and a discharge performance decrease rate after storage of 15%.
Example 6
A method for preparing a zinc paste, which is substantially the same as example 1, except that the mass ratio of PAA to BPEI is 80, and the weight-average molecular weight of BPEI is 45000g/mol.
The prepared zinc paste comprises PAA, BPEI, KOH solution, indium hydroxide and zinc powder; the zinc powder is uniformly dispersed without obvious sinking and is combined with amino on a BPEI branched chain through a hydrogen bond; carboxyl on the PAA main chain and amino on the BPEI branched chain generate ionic bond crosslinking and covalent bond crosslinking to form a three-dimensional network structure with a plurality of branched chains.
The LR6 battery made of the calamine cream had an internal resistance of 60 Ω, a discharge frequency of 164 times, and a discharge performance decrease rate after storage of 12.8%.
Example 7
A calamine cream preparation method, basically the same as example 6, except that the weight average molecular weight of BPEI is 75000g/mol.
The prepared zinc paste comprises PAA, BPEI, KOH solution, indium hydroxide and zinc powder; the zinc powder is uniformly dispersed without obvious sinking and is combined with amino on a BPEI branched chain through hydrogen bonds; carboxyl on the PAA main chain and amino on the BPEI branched chain generate ionic bond crosslinking and covalent bond crosslinking to form a three-dimensional network structure with a plurality of branched chains.
The LR6 battery made of the calamine cream had an internal resistance of 67 Ω, a discharge frequency of 146 times, and a discharge performance decrease rate after storage of 12.4%.
Example 8
A process for preparing a zinc paste, substantially as in example 6, except that the total content of PAA and BPEI in the mixed solution is 1wt%, and the weight average molecular weight of BPEI is 60000g/mol.
The prepared zinc paste comprises PAA, BPEI, KOH solution, indium hydroxide and zinc powder; the zinc powder is uniformly dispersed, the sedimentation rate is 7.8%, and the zinc powder is combined with amino on a BPEI branched chain through hydrogen bonds; carboxyl on the PAA main chain and amino on the BPEI branched chain generate ionic bond crosslinking and covalent bond crosslinking to form a three-dimensional network structure with a plurality of branched chains.
The LR6 battery made of calamine cream had an internal resistance of 78 Ω, a number of discharges of 129 times, and a rate of decrease in discharge performance after storage was 18.7%.
Example 9
A process for preparing a zinc paste substantially as in example 8, except that the total content of PAA and BPEI in the mixture is 10% by weight.
The prepared zinc paste comprises PAA, BPEI, KOH solution, indium hydroxide and zinc powder; the zinc powder is uniformly dispersed without obvious sinking and is combined with amino on a BPEI branched chain through a hydrogen bond; carboxyl on the PAA main chain and amino on the BPEI branched chain generate ionic bond crosslinking and covalent bond crosslinking to form a three-dimensional network structure with a plurality of branched chains.
The LR6 battery made of calamine cream had an internal resistance of 77 Ω, a number of discharges of 131, and a rate of decrease in discharge performance after storage of 17.6%.
Example 10
A process for preparing a zinc paste, substantially as described in example 8, except that PAAS is substituted for PAA and the total content of PAAS and BPEI in the mixture is 5% by weight.
The prepared zinc paste comprises PAAS, BPEI, KOH solution, indium hydroxide and zinc powder; the zinc powder is uniformly dispersed without obvious sinking and is combined with amino on a BPEI branched chain through a hydrogen bond; carboxyl on the PAAS main chain and amino on the BPEI branched chain generate ionic bond crosslinking and covalent bond crosslinking to form a three-dimensional network structure with a large number of branched chains.
The LR6 battery made of calamine cream had an internal resistance of 58 Ω, a discharge frequency of 167 times, and a discharge performance decrease rate after storage of 14.4%.
Comparative example 2
A method of making a calamine cream, substantially as in example 10, except that no BPEI is added during the preparation.
The prepared calamine cream comprises PAAS, KOH solution, indium hydroxide and zinc powder; the zinc powder had poor dispersibility and a settling rate of 9.3%.
The LR6 battery made of calamine cream had an internal resistance of 80 Ω, a discharge frequency of 124 times, and a discharge performance degradation rate of 24.7% after storage.
Compared with example 10, the zinc powder dispersibility and suspension property of the calamine paste of comparative example 2 are inferior to those of example 10, and the cell obtained has inferior discharge times and discharge property decrease rate after storage as compared with example 10, because the carboxyl group on the main chain of PAAS and the amino group on the BPEI branch chain in example 10 are subjected to ionic bond crosslinking and covalent bond crosslinking to form a three-dimensional network structure with a large number of branch chains.
From examples 1 to 5, it can be seen that in the range of the mass ratio of the PAA to the BPEI of 97 to 80; in the range of the mass ratio of the PAA to the BPEI being 70-60, along with the improvement of the mass ratio of the BPEI, the suspension performance of the zinc powder is reduced, the internal resistance of an LR6 battery made of the zinc paste is reduced, the discharge frequency is improved, and the discharge performance reduction rate after storage is reduced, because the BPEI is a hyperbranched high polymer material with smaller molecular weight, when the mass ratio occupied by the composite gel is too large, the viscosity of the gel is reduced, the uniform dispersion of the zinc powder is facilitated in the paste activating process, the resistance of a new battery is favorably reduced, the discharge frequency of the new battery is improved, but the suspension performance of the zinc powder is also reduced, and the discharge frequency after long-term storage is influenced.
The total content of the PAA and the BPEI in the mixed liquid is 2 to 10 weight percent. From the examples 8 and 9, it can be seen that when the total content of the PAA and BPEI in the mixed solution is 1wt%, the viscosity becomes small, and in the paste activating process, the zinc powder is more favorably and uniformly dispersed, the resistance of a new battery is favorably reduced, the discharge frequency of the new battery is improved, but the suspension property of the zinc powder is also reduced, and the discharge frequency of the new battery after long-term storage is influenced; when the total content of the PAA and the BPEI in the mixed solution is 10wt%, the viscosity is increased, and the zinc powder is not beneficial to uniform dispersion in the paste activating process, the resistance of a new battery is not beneficial to reduction, the discharge frequency of the new battery is reduced, but the suspension property of the zinc powder is also improved, and the discharge frequency of the new battery after long-term storage is improved. In order to balance the properties, the invention prefers that the total content of PAA and BPEI in the mixed solution is 5wt%.
Example 11
A preparation method of calamine cream comprises the following specific processes:
at room temperature, firstly adding a mixture of PAA and PAAS with the mass ratio of 1 to 45wt% NaOH solution and uniformly stirring, then adding BPEI with the weight-average molecular weight of 50000g/mol and uniformly stirring to obtain a mixed solution; finally, adding indium hydroxide and zinc powder with the apparent weight ratio of 5g/mL, heating to 80 ℃, and uniformly stirring to obtain zinc paste; wherein the total content of PAA, PAAS and BPEI in the mixed solution is 7wt%; the ratio of the sum of the masses of PAA and PAAs to the mass of BPEI is 97; the mass ratio of the zinc powder to the mixed solution is 2.5; the mass ratio of the indium hydroxide to the zinc powder is 0.05.
The prepared zinc paste comprises PAA, PAAS, BPEI, naOH solution, indium hydroxide and zinc powder; the zinc powder is uniformly dispersed, the sedimentation rate is 6.6%, and the zinc powder is combined with amino on a BPEI branched chain through hydrogen bonds; carboxyl on the main chains of PAA and PAAS and amino on the BPEI branched chains generate ionic bond crosslinking and covalent bond crosslinking to form a three-dimensional network structure with a large number of branched chains.
The LR6 battery made of calamine cream had an internal resistance of 72 Ω, a discharge frequency of 134 times, and a discharge performance decrease rate after storage of 15%.
Example 12
A preparation method of a zinc paste comprises the following specific steps:
at room temperature, firstly adding PAAS into a 40wt% NaOH solution, uniformly stirring, then adding BPEI with the weight-average molecular weight of 60000g/mol, and uniformly stirring to obtain a mixed solution; finally, adding indium hydroxide and zinc powder with the apparent weight ratio of 4g/mL, heating to 90 ℃, and uniformly stirring to obtain zinc paste; wherein the total content of PAAS and BPEI in the mixed solution is 4wt%; the mass ratio of the PAAS to the BPEI is 97; the mass ratio of the zinc powder to the mixed solution is 1.7; the mass ratio of the indium hydroxide to the zinc powder is 0.05.
The prepared zinc paste comprises PAAS, BPEI, naOH solution, indium hydroxide and zinc powder; the zinc powder is uniformly dispersed, the sedimentation rate is 7.2 percent, and the zinc powder is combined with amino on a BPEI branched chain through a hydrogen bond; carboxyl on the PAAS main chain and amino on the BPEI branched chain generate ionic bond crosslinking and covalent bond crosslinking to form a three-dimensional network structure with a large number of branched chains.
The LR6 battery made of the calamine cream had an internal resistance of 76 Ω, a discharge frequency of 134 times, and a discharge performance decrease rate after storage of 16.9%.

Claims (9)

1. A calamine cream gel is characterized by comprising a main substance and an auxiliary substance; the main substance is PAA and/or PAAS; the auxiliary substance is BPEI.
2. The calamine cream gel of claim 1 wherein the BPEI has a weight average molecular weight of 45000-75000 g/mol.
3. The calamine cream gel of claim 1 or 2, wherein the mass ratio of the main material to the auxiliary material is 97 to 60.
4. A process for preparing a calamine cream using a calamine cream gel as claimed in any one of claims 1 to 3 wherein said primary material is first added to said electrolyte and stirred uniformly, then said secondary material is added and stirred uniformly to obtain a mixed solution, and finally said mixed solution is heated to 70-90 ℃ after adding the corrosion inhibitor and zinc powder and stirred uniformly to obtain the calamine cream.
5. The method of claim 4, wherein the electrolyte is a KOH solution; the corrosion inhibitor is indium hydroxide.
6. The method as defined in claim 4, wherein the zinc powder has an apparent weight ratio of 2 to 4g/mL.
7. The method of claim 4, wherein the electrolyte has a concentration of 20 to 45wt%; the total content of the main substances and the auxiliary substances in the mixed solution is 1 to 10 weight percent; the mass ratio of the zinc powder to the mixed solution is 1.5-2.5; the mass ratio of the corrosion inhibitor to the zinc powder is 0.05.
8. The calamine cream produced by the method of any of claims 4 to 7, comprising said main substance, said auxiliary substance, an electrolyte, a corrosion inhibitor and zinc powder; the zinc powder is uniformly dispersed and is combined with the amino on the auxiliary substance branched chain through a hydrogen bond; and the carboxyl on the main chain of the main substance and the amino on the branched chain of the auxiliary substance generate ionic bond crosslinking and covalent bond crosslinking to form a three-dimensional network structure with branched chains.
9. The calamine cream of claim 8, wherein the LR6 battery made of calamine cream has an internal resistance of 49 to 78 Ω, a number of discharges of 129 to 174, and a rate of decrease in discharge performance after storage of 10.2 to 18.7%.
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