CN102044669A - Zinc cathode active substance of zinc-nickel secondary battery and preparation method and application method thereof - Google Patents
Zinc cathode active substance of zinc-nickel secondary battery and preparation method and application method thereof Download PDFInfo
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Abstract
The invention discloses a zinc cathode active substance of a zinc-nickel secondary battery and a preparation method and application method thereof. The preparation method of the active substance comprises the following steps: (1) dissolving In2O3 in concentrated hydrochloric acid; (2) dissolving ZnCl2 in deionized water and adding dispersant; (3) mixing the two solutions and diluting with deionized water; (4) adding ammonia water dropwise into the mixed dilute solution to regulate pH while strongly stirring mechanically, then stirring and aging; (5) performing ultrasonic dispersion on the aged liquid, transferring to a hydro-thermal reaction kettle and putting the reaction kettle in an oven for heat preservation; and (6) filtering, washing and drying the precipitate, and calcining at certain temperature to obtain indium-doped zinc oxide. The active substance can reduce the deformation of the zinc cathode, suppress the dissolution of the active substance of the zinc cathode and prolong the cyclic service life of the zinc-nickel secondary battery.
Description
Technical field
The present invention relates to a kind of zinc negative electrode active material and methods for making and using same thereof of zinc-nickel secondary batteries.
Background technology
Advantage such as the alkali zinc nickel secondary cell has that specific energy is big, specific power is high, stable operating voltage, abundant raw materials are nontoxic and people's attention extremely, these advantages also make zinc-nickel secondary batteries become the strong competitor of new generation of green electrokinetic cell.But there is the short defective of cycle life in such battery, causes its practicability to be subjected to no small resistance.Cause the short-life main cause of zinc-nickel secondary batteries to be that zinc electrode exists electrode deformation, passivation, zinc dendrite, problem such as corrosion certainly in cyclic process.In order to address these problems, people have done a lot of researchs.Ca (OH)
2Generally believed it is a kind of effective zinc cathode additive agent, this is because in battery discharge procedure, Ca (OH)
2Can form zincic acid calcium with the ZnO reaction, the solubility of this material in alkaline electrolyte is very little, thereby can suppress the migration of zinc negative electrode active material ZnO to electrolyte, solves the problem of zinc negative pole to a certain extent.But the Ca of required adding (OH)
2Measure greatlyyer, reduced the energy density and the capacity density of battery.02134316.0 proposition of patent directly with zincic acid calcium as negative electrode active material, but also there is battery capacity problem on the low side in zincic acid calcium.Therefore, be that negative electrode active material still is the selection of capacity zinc nickel secondary batteries with ZnO.
Zinc oxide is carried out the problem that surface modification both can solve the zinc negative pole preferably, can not make a big impact simultaneously battery capacity.Patent CN 101325256A has mentioned with the surface and has coated Sn
6O
4(OH)
4ZnO as negative electrode active material, patent CN101533908A has mentioned with Bi
2O
3The ZnO that modifies with the nanometer bismuth composite surface of BiO is as the negative material of zinc-base battery, and the both has obtained effect preferably.But these methods all are that the ZnO material is carried out surface treatment, and its performance relies on the electrical property of ZnO body to a great extent, and also there is certain problem in the mass preparation process.Therefore, the study on the modification to zinc oxide material is still a content that is worth making great efforts research.
Summary of the invention
The objective of the invention is to design a kind of zinc negative electrode active material and methods for making and using same thereof that the distortion of zinc negative pole, the negative electrode active material dissolving of inhibition zinc and prolongation zinc-nickel secondary batteries recycle the life-span that reduce.
The preparation method of a kind of zinc negative electrode active material of zinc-nickel secondary batteries (being the indium doping zinc-oxide) may further comprise the steps:
(1) with the analytically pure In of 0.5-10 weight portion
2O
3Be dissolved in the 12mol/L concentrated hydrochloric acid of 30-60 weight portion;
(2) with the analytically pure ZnCl of 60-120 weight portion
2Be dissolved in the deionized water of 200-500 weight portion, and add the dispersant of 0.1-1 weight portion;
(3) above-mentioned two kinds of solution are mixed, doubly with deionized water dilution 3-15;
(4) under strong mechanical agitation, be 6.0-9.0 to above-mentioned mixed diluting solution dropping ammonia to pH value of solution, continue to stir 10-60min, ageing 0.5-2.0h;
(5) with the ultrasonic dispersion of above-mentioned ageing liquid 5-30min, after be transferred in the hydrothermal reaction kettle, the baking oven of reactor being put into 150-250 ℃ is incubated 3.0-6.0h;
(6) the gained precipitation is filtered, washed, and, calcine 1.5-3.5h down for 450-600 ℃ and get final product at 50-100 ℃ of following dry 2.0-5.0h.
Described dispersant comprises one or more in neopelex, calgon, softex kw, the fatty acid polyethylene glycol ester.
Described zinc negative electrode active material is applied to prepare the zinc negative pole of zinc-nickel secondary batteries; Specifically may further comprise the steps:
(1) other zinc compounds of the conductive agent of the described zinc negative electrode active material of 75-85 weight portion, 4-6 weight portion, 7-27 weight portion is carried out mechanical mixture and obtain the negative material mixture;
(2) dispersant with the 0.02-5 weight portion is dissolved in the distilled water of 30-45 weight portion;
(3) the negative material mixture that step (1) is obtained joins in step (2) the gained solution, adds binder solution then under strong agitation, and the negative material mixture weight that binder solution and step (1) obtain is than being 1-6: 100; Obtain uniform mobile zinc cathode size;
(4) the zinc cathode size with step (3) is coated on zinc electrode collector two sides and oven dry, is cut into the zinc negative pole finished product pole piece of certain specification.
Described conductive agent is the mixture of electrically conductive graphite and aluminium powder, glass putty or copper powder.
Described other zinc compounds are the mixture of zinc powder and zinc-indium, zinc-indium-bismuth, zinc-Xi or zinc-Sn-In alloy powder.
Described dispersant comprises one or more in neopelex, softex kw, inferior sodium phosphate, hexamethylenetetramine, the polyethylene glycol.
Described binding agent is one or more of Sodium Polyacrylate, polypropylene, polyethylene, polyaniline, polypyrrole, butadiene-styrene rubber.
The invention has the advantages that in charging process, the indium ion on the Zinc oxide particles surface of chemical doping indium can preferentially be reduced to indium metal, this indium metal is covered in the Zinc oxide particles surface, has isolated zinc oxide and the direct of alkaline electrolyte to a certain extent and has contacted, and has slowed down the migration of zinc oxide.Indium metal has higher overpotential of hydrogen evolution simultaneously, can effectively suppress the corrosion certainly of zinc negative pole.The satisfactory electrical conductivity of indium metal also can improve the conductivity of zinc negative pole, weakens the ohmic polarization of zinc negative pole, can guarantee the excellent electric contact between active material particle simultaneously.These factors all help the efficient release of zinc capacity of negative plates, improve the cycle life of zinc-nickel secondary batteries greatly.
The present invention compared with prior art has the preparation method and is fit to advantages such as large-scale production, controlled, the prepared zinc-nickel secondary batteries of material pattern have extended cycle life.
Description of drawings
Fig. 1 is the XRD figure of the zinc oxide of the zinc negative electrode active material chemical doping indium for preparing of the present invention;
Fig. 2 is the SEM figure of the zinc oxide of the zinc negative electrode active material chemical doping indium for preparing of the present invention.
Embodiment
Be intended to further specify the present invention below in conjunction with embodiment, and unrestricted the present invention.
Specific embodiments of the invention have following:
Embodiment 1
Analytically pure In with 1.5 weight portions
2O
3Be dissolved in the 12mol/L concentrated hydrochloric acid of 50 weight portions, with the analytically pure ZnCl of 98 weight portions
2Be dissolved in the deionized water of 200 weight portions, and add the neopelex of 0.5 weight portion, above-mentioned two kinds of solution are fully mixed and with 10 times of deionized water dilutions, adding ammoniacal liquor regulator solution pH then under strong mechanical agitation is 7.0, continue to stir 15min, ageing 1h, ultrasonic dispersion 10min, after be transferred in the hydrothermal reaction kettle, the baking oven of reactor being put into 180 ℃ is incubated 4h, at last precipitation is filtered, washed, and, calcine 2h down for 500 ℃ and promptly get the indium doping zinc-oxide at 60 ℃ of following dry 4h.With the 0.1g neopelex, 0.1g softex kw places beaker, add 30g distilled water, beaker placed on the electronic heating stirrer slowly stir, after treating that neopelex and softex kw dissolve fully, with the zinc oxide of 96g chemical doping indium and the compound of other zinc, 3.5g electrically conductive graphite, 0.5g aluminium powder adds in the above-mentioned beaker solution, after stirring, adding 3g concentration is 50% SBR emulsion, stirring obtains uniform mobile cathode size, with tensile pulp machine this slurry is coated to copper mesh two sides and dry, makes the zinc negative pole finished product pole piece that some dimensionss are 105mm * 36mm through shearing.The anodal dimensions that adopts is the anodal commercial pole piece of nickel of 50mm * 30mm.To accompany microporous polypropylene membrane in the middle of the above-mentioned zinc negative pole, nickel positive pole and the polypropylene non-woven fabric membrane coil becomes battery battery core around multi-turn, and in the AA type battery copper facing box hat of packing into, through slot rolling, spot welding, the mixed electrolytic solution that contains 5M KOH, 0.8M NaOH, 0.4M LiOH and oxidized zincification is injected in the back, seals and is assembled into AA type sealing cylinder shape zinc-nickel secondary batteries.
Embodiment 2
Analytically pure In with 5 weight portions
2O
3Be dissolved in the 12mol/L concentrated hydrochloric acid of 50 weight portions, with the analytically pure ZnCl of 94.5 weight portions
2Be dissolved in the deionized water of 200 weight portions, and add the neopelex of 0.5 weight portion, above-mentioned two kinds of solution are fully mixed and with 10 times of deionized water dilutions, adding ammoniacal liquor regulator solution pH then under strong mechanical agitation is 7.0, continue to stir 15min, ageing 1h, ultrasonic dispersion 10min, after be transferred in the hydrothermal reaction kettle, the baking oven of reactor being put into 180 ℃ is incubated 4h, at last precipitation is filtered, washed, and, calcine 2h down for 500 ℃ and promptly get the indium doping zinc-oxide at 60 ℃ of following dry 4h.With the 0.1g neopelex, 0.1g softex kw places beaker, add 30g distilled water, beaker placed on the electronic heating stirrer slowly stir, after treating that neopelex and softex kw dissolve fully, with the zinc oxide of 96g chemical doping indium and the compound of other zinc, 3.5g electrically conductive graphite, 0.5g aluminium powder adds in the above-mentioned beaker solution, after stirring, adding 3g concentration is 50% SBR emulsion, stirring obtains uniform mobile cathode size, with tensile pulp machine this slurry is coated to copper mesh two sides and dry, makes the zinc negative pole finished product pole piece that some dimensionss are 105mm * 36mm through shearing.Above-mentioned zinc negative pole is assembled into AA type sealing cylinder shape zinc-nickel secondary batteries according to embodiment 1 identical method.
Embodiment 3
Analytically pure In with 7 weight portions
2O
3Be dissolved in the 12mol/L concentrated hydrochloric acid of 50 weight portions, with the analytically pure ZnCl of 92.5 weight portions
2Be dissolved in the deionized water of 200 weight portions, and add the neopelex of 0.5 weight portion, above-mentioned two kinds of solution are fully mixed and with 10 times of deionized water dilutions, adding ammoniacal liquor regulator solution pH then under strong mechanical agitation is 7.0, continue to stir 15min, ageing 1h, ultrasonic dispersion 10min, after be transferred in the hydrothermal reaction kettle, the baking oven of reactor being put into 180 ℃ is incubated 4h, at last precipitation is filtered, washed, and, calcine 2h down for 500 ℃ and promptly get the indium doping zinc-oxide at 60 ℃ of following dry 4h.With the 0.1g neopelex, 0.1g softex kw places beaker, add 30g distilled water, beaker placed on the electronic heating stirrer slowly stir, after treating that neopelex and softex kw dissolve fully, with the zinc oxide of 96g chemical doping indium and the compound of other zinc, 3.5g electrically conductive graphite, 0.5g aluminium powder adds in the above-mentioned beaker solution, after stirring, adding 3g concentration is 50% SBR emulsion, stirring obtains uniform mobile cathode size, with tensile pulp machine this slurry is coated to copper mesh two sides and dry, makes the zinc negative pole finished product pole piece that some dimensionss are 105mm * 36mm through shearing.Above-mentioned zinc negative pole is assembled into AA type sealing cylinder shape zinc-nickel secondary batteries according to embodiment 1 identical method.
Embodiment 4
Analytically pure In with 9 weight portions
2O
3Be dissolved in the 12mol/L concentrated hydrochloric acid of 50 weight portions, with the analytically pure ZnCl of 90.5 weight portions
2Be dissolved in the deionized water of 200 weight portions, and add the neopelex of 0.5 weight portion, above-mentioned two kinds of solution are fully mixed and with 10 times of deionized water dilutions, adding ammoniacal liquor regulator solution pH then under strong mechanical agitation is 7.0, continue to stir 15min, ageing 1h, ultrasonic dispersion 10min, after be transferred in the hydrothermal reaction kettle, the baking oven of reactor being put into 180 ℃ is incubated 4h, at last precipitation is filtered, washed, and, calcine 2h down for 500 ℃ and promptly get the indium doping zinc-oxide at 60 ℃ of following dry 4h.With the 0.1g neopelex, 0.1g softex kw places beaker, add 30g distilled water, beaker placed on the electronic heating stirrer slowly stir, after treating that neopelex and softex kw dissolve fully, with the zinc oxide of 96g chemical doping indium and the compound of other zinc, 3.5g electrically conductive graphite, 0.5g aluminium powder adds in the above-mentioned beaker solution, after stirring, adding 3g concentration is 50% SBR emulsion, stirring obtains uniform mobile cathode size, with tensile pulp machine this slurry is coated to copper mesh two sides and dry, makes the zinc negative pole finished product pole piece that some dimensionss are 105mm * 36mm through shearing.Above-mentioned zinc negative pole is assembled into AA type sealing cylinder shape zinc-nickel secondary batteries according to embodiment 1 identical method.
The comparative example 1
Compound, 3.5g electrically conductive graphite, the 0.5g aluminium powder of 96g zinc oxide and other zinc are added in the above-mentioned beaker solution, after stirring, adding 3g concentration is 50% SBR emulsion, stirring obtains uniform mobile cathode size, with tensile pulp machine this slurry is coated to copper mesh two sides and dry, makes the zinc negative pole finished product pole piece that some dimensionss are 105mm * 36mm through shearing.Above-mentioned zinc negative pole is assembled into AA type sealing cylinder shape zinc-nickel secondary batteries according to embodiment 1 identical method.
The zinc oxide product test of chemical doping indium:
In the foregoing description the XRD diffraction test result of the zinc oxide product of chemical doping indium as shown in Figure 1, the SEM test result is as shown in Figure 2.Fig. 1 is compared with the standard diffraction maximum of zinc oxide, find that its data and base peak are very identical, illustrate that the element indium has well mixed zinc oxide lattice, obtained the higher indium doping zinc-oxide product of purity.Can see that by Fig. 2 the indium doping zinc-oxide product that obtains in the foregoing description presents irregular sheet pattern, particle size range broad.
Battery performance test:
The battery that the foregoing description and comparative example assembling obtains is following activation processing: 45mA charging 13h, shelves 10min, the back is discharged to 1.4V with 90mA; The 90mA 12h that charges shelves 10min, and the back is discharged to 1.4V with 225mA; The 225mA 11h that charges finishes activation.Discharge and recharge with the 1C electric current under room temperature (25 ± 2 ℃) then, the cycle life of zinc-nickel secondary batteries is measured in circulation.The test cell circulation stops test later on 100 times.The results are shown in table 1.Can see from the result of table 1, zinc negative pole of the present invention adopts the indium doping zinc-oxide can suppress the migration of negative electrode active material largely, alleviate the problem on deformation that the zinc negative pole causes because of the active material dissolution-deposition in cyclic process, increase substantially the cycle life of sealed Zn-Ni secondary cell.
Table 1AA type (450mAh) sealing cylinder shape zinc-nickel secondary batteries performance
Claims (9)
1. the preparation method of the zinc negative electrode active material of a zinc-nickel secondary batteries is characterized in that, may further comprise the steps:
(1) with the In of 0.5-10 weight portion
2O
3Be dissolved in the 12mol/L concentrated hydrochloric acid of 30-60 weight portion;
(2) with the analytically pure ZnCl of 60-120 weight portion
2Be dissolved in the deionized water of 200-500 weight portion, and add the dispersant of 0.1-1 weight portion;
(3) above-mentioned two kinds of solution are mixed, doubly with deionized water dilution 3-15;
(4) under strong mechanical agitation, be 6.0-9.0 to above-mentioned mixed diluting solution dropping ammonia to pH value of solution, continue to stir 10-60min, ageing 0.5-2.0h;
(5) with the ultrasonic dispersion of above-mentioned ageing liquid 5-30min, after be transferred in the hydrothermal reaction kettle, the baking oven of reactor being put into 150-250 ℃ is incubated 3.0-6.0h;
(6) the gained precipitation is filtered, washed, and, calcine 1.5-3.5h down for 450-600 ℃ and get final product at 50-100 ℃ of following dry 2.0-5.0h.
2. preparation method according to claim 1 is characterized in that described dispersant comprises one or more in neopelex, calgon, softex kw, the fatty acid polyethylene glycol ester.
3. the zinc negative electrode active material of a zinc-nickel secondary batteries is characterized in that, is the material that is prepared by claim 1 or 2 described methods.
4. the described zinc negative electrode active material of claim 3 is applied to prepare the zinc negative pole of zinc-nickel secondary batteries.
5. application process according to claim 4 is characterized in that, may further comprise the steps:
(1) other zinc compounds of the conductive agent of the described zinc negative electrode active material of 75-85 weight portion, 4-6 weight portion, 7-27 weight portion is carried out mechanical mixture and obtain the negative material mixture;
(2) dispersant with the 0.02-5 weight portion is dissolved in the distilled water of 30-45 weight portion;
(3) the negative material mixture that step (1) is obtained joins in step (2) the gained solution, under strong agitation, add binder solution then, the negative material mixture weight that binder solution and step (1) obtain is than being 1-6: 100, obtain uniform mobile zinc cathode size;
(4) the zinc cathode size with step (3) is coated on zinc electrode collector two sides and oven dry, is cut into the zinc negative pole finished product pole piece of certain specification.
6. application process according to claim 5 is characterized in that, described conductive agent is the mixture of electrically conductive graphite and aluminium powder, glass putty or copper powder.
7. application process according to claim 5 is characterized in that, described other zinc compounds are the mixture of zinc powder and zinc-indium, zinc-indium-bismuth, zinc-Xi or zinc-Sn-In alloy powder.
8. application process according to claim 5 is characterized in that described dispersant comprises one or more in neopelex, softex kw, inferior sodium phosphate, hexamethylenetetramine, the polyethylene glycol.
9. application process according to claim 5 is characterized in that, described binding agent is one or more of Sodium Polyacrylate, polypropylene, polyethylene, polyaniline, polypyrrole, butadiene-styrene rubber.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102208630A (en) * | 2011-05-16 | 2011-10-05 | 卢国骥 | Method for preparing zinc cathode sheet of alkaline zinc base secondary battery |
| CN102263261A (en) * | 2011-06-21 | 2011-11-30 | 中南大学 | Method for application of zinc-aluminum hydrotalcite in preparation of zinc anode of zinc-nickel secondary battery |
| CN102867943A (en) * | 2011-07-04 | 2013-01-09 | 东台天祥新能源有限公司 | Preparation method and application method for zinc cathode active material of zinc-nickel secondary battery |
| CN104200874A (en) * | 2014-09-05 | 2014-12-10 | 铜陵市毅远电光源有限责任公司 | Conductive silver paste added with manganese oxide ores and production method of conductive silver paste |
| CN106876713A (en) * | 2015-12-11 | 2017-06-20 | 浙江野马电池有限公司 | Alkaline manganese battery cathode additive |
| CN110289395A (en) * | 2019-07-01 | 2019-09-27 | 超威电源有限公司 | A kind of lotion and preparation method thereof for Zinc-nickel battery negative |
| CN110970590A (en) * | 2019-12-18 | 2020-04-07 | 江苏厚生新能源科技有限公司 | Ceramic coating slurry, preparation method thereof, lithium battery diaphragm and lithium ion battery |
| CN111009653A (en) * | 2019-12-10 | 2020-04-14 | 河南创力新能源科技股份有限公司 | Preparation method of zinc cathode material of zinc-nickel secondary battery |
| CN111463408A (en) * | 2020-03-18 | 2020-07-28 | 山东合泰新能源有限公司 | Preparation method of coating type zinc electrode |
| CN111916744A (en) * | 2020-07-31 | 2020-11-10 | 中南大学 | Liquid metal composite cathode of zinc ion battery and preparation method and application thereof |
| CN112038602A (en) * | 2020-09-02 | 2020-12-04 | 河南超力新能源有限公司 | Composite negative electrode material for zinc-based secondary battery, preparation method of composite negative electrode material and zinc-based secondary battery |
| CN112824323A (en) * | 2019-11-21 | 2021-05-21 | 中国科学院大连化学物理研究所 | Indium-doped zinc oxide composite reduced graphene oxide material, and preparation and application thereof |
| CN114551873A (en) * | 2020-11-26 | 2022-05-27 | 中国科学院大连化学物理研究所 | Bismuth trioxide modified indium-doped zinc oxide material and preparation and application thereof |
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| CN1482698A (en) * | 2003-07-17 | 2004-03-17 | 武汉大学 | Method for preparing secondary basic zinc electrode material |
| CN101071850A (en) * | 2007-05-25 | 2007-11-14 | 新乡联达华中电源有限公司 | Zinc cathode of secondary zinc-nickel battery and preparation method thereof |
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Patent Citations (2)
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| CN1482698A (en) * | 2003-07-17 | 2004-03-17 | 武汉大学 | Method for preparing secondary basic zinc electrode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102208630A (en) * | 2011-05-16 | 2011-10-05 | 卢国骥 | Method for preparing zinc cathode sheet of alkaline zinc base secondary battery |
| CN102263261A (en) * | 2011-06-21 | 2011-11-30 | 中南大学 | Method for application of zinc-aluminum hydrotalcite in preparation of zinc anode of zinc-nickel secondary battery |
| CN102867943A (en) * | 2011-07-04 | 2013-01-09 | 东台天祥新能源有限公司 | Preparation method and application method for zinc cathode active material of zinc-nickel secondary battery |
| CN104200874A (en) * | 2014-09-05 | 2014-12-10 | 铜陵市毅远电光源有限责任公司 | Conductive silver paste added with manganese oxide ores and production method of conductive silver paste |
| CN106876713A (en) * | 2015-12-11 | 2017-06-20 | 浙江野马电池有限公司 | Alkaline manganese battery cathode additive |
| CN106876713B (en) * | 2015-12-11 | 2019-09-06 | 浙江野马电池股份有限公司 | Alkaline manganese battery cathode additive |
| CN110289395A (en) * | 2019-07-01 | 2019-09-27 | 超威电源有限公司 | A kind of lotion and preparation method thereof for Zinc-nickel battery negative |
| CN112824323A (en) * | 2019-11-21 | 2021-05-21 | 中国科学院大连化学物理研究所 | Indium-doped zinc oxide composite reduced graphene oxide material, and preparation and application thereof |
| CN111009653A (en) * | 2019-12-10 | 2020-04-14 | 河南创力新能源科技股份有限公司 | Preparation method of zinc cathode material of zinc-nickel secondary battery |
| CN111009653B (en) * | 2019-12-10 | 2022-12-09 | 河南创力新能源科技股份有限公司 | Preparation method of zinc cathode material of zinc-nickel secondary battery |
| CN110970590A (en) * | 2019-12-18 | 2020-04-07 | 江苏厚生新能源科技有限公司 | Ceramic coating slurry, preparation method thereof, lithium battery diaphragm and lithium ion battery |
| CN111463408A (en) * | 2020-03-18 | 2020-07-28 | 山东合泰新能源有限公司 | Preparation method of coating type zinc electrode |
| CN111916744A (en) * | 2020-07-31 | 2020-11-10 | 中南大学 | Liquid metal composite cathode of zinc ion battery and preparation method and application thereof |
| CN111916744B (en) * | 2020-07-31 | 2022-03-08 | 中南大学 | Liquid metal composite cathode of zinc ion battery and preparation method and application thereof |
| CN112038602A (en) * | 2020-09-02 | 2020-12-04 | 河南超力新能源有限公司 | Composite negative electrode material for zinc-based secondary battery, preparation method of composite negative electrode material and zinc-based secondary battery |
| CN112038602B (en) * | 2020-09-02 | 2021-11-16 | 河南超力新能源有限公司 | Composite negative electrode material for zinc-based secondary battery, preparation method of composite negative electrode material and zinc-based secondary battery |
| CN114551873A (en) * | 2020-11-26 | 2022-05-27 | 中国科学院大连化学物理研究所 | Bismuth trioxide modified indium-doped zinc oxide material and preparation and application thereof |
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