CN108232333A - A kind of low-temperature electrolyte of Ni-MH battery - Google Patents

A kind of low-temperature electrolyte of Ni-MH battery Download PDF

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Publication number
CN108232333A
CN108232333A CN201711479562.9A CN201711479562A CN108232333A CN 108232333 A CN108232333 A CN 108232333A CN 201711479562 A CN201711479562 A CN 201711479562A CN 108232333 A CN108232333 A CN 108232333A
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calcium
electrolyte
low
battery
potassium hydroxide
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CN201711479562.9A
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Inventor
肖中平
何立辉
李兴松
王华锋
邓通
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Dongguan City Industrial Co Ltt
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Dongguan City Industrial Co Ltt
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/26—Selection of materials as electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/30—Nickel accumulators
    • 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
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0014—Alkaline electrolytes
    • 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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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Secondary Cells (AREA)

Abstract

The present invention provides a kind of low-temperature electrolytes of Ni-MH battery, including electrolyte and additive, the electrolyte includes potassium hydroxide and lithium hydroxide, the additive includes soluble calcium salt, nonionic surfactant, inorganic inhibitor, and the concentration of the additive each component in the electrolytic solution is respectively：0.1 1mol/L of soluble calcium salt；0.05 0.15mol/L of nonionic surfactant；0.01 0.08mol/L of inorganic inhibitor.The present invention provides low-temperature electrolyte, is precipitated at 40 DEG C without potassium hydroxide crystal, and appropriate positive and negative pole material is coordinated to make battery testing, at 40 DEG C standard charge and discharge still can reach 80% rated capacity.

Description

A kind of low-temperature electrolyte of Ni-MH battery
Technical field
The present invention relates to Ni-MH battery fields, and in particular to a kind of low-temperature electrolyte of Ni-MH battery.
Background technology
Ni-MH battery is a kind of accumulator being made by two kinds of main materials of hydrogen bearing alloy and spherical hickelous nydroxide, Power Reserve is than nickel-cadmium cell higher, and weight ratio nickel-cadmium cell is light, and service life is long, and memory-less effect, due to ni-mh electricity Pond is free of cadmium element, environmentally safe.Therefore, Ni-MH battery in today's society by as a kind of environmentally protective chargeable Battery and be widely used.The shortcomings that Ni-MH battery is that price is more expensive than nickel-cadmium cell, performance ratio lithium battery will it is poor, Ni-MH battery without Memory effect.Anode of nickel-metal hydride battery active material is nickel hydroxide, and negative electrode active material is metal oxide, also referred to as stores hydrogen and closes Gold, electrolyte are potassium hydroxide.During charging, cathode absorbs hydrogen atom, and in the alloy, anode becomes hydrogen by hickelous nydroxide for storage Nickel oxide (NiOOH) and H2O；Active hydrogen atom is released from alloy during electric discharge, is converted into water, and anode is become by nickel hydroxide Into hickelous nydroxide.
With the sustainable development of science and technology, the scientific investigation activity on some polar regions and plateau is increasingly frequent, is badly in need of being resistant to extreme severe cold Battery product, at present major part Ni-MH battery can not meet the requirements.General Ni-MH battery at low temperature charge and discharge when, due to work Property species activity die down, cell voltage is caused to reduce, internal pressure raising, cause battery that can not use.Then, low-temperature electrolyte is ground Study carefully and come into being.When the temperature is too low, the alkaline matter in Ni-MH battery electrolyte will crystallize precipitation, cause in electrolyte Molar concentration further reduces, so that sustained activity dies down, vicious circle or even battery is caused to scrap.
Therefore, there is an urgent need for being improved on the electrolyte, make its alkaline electrolyte that crystallization will not be precipitated because of low temperature, make it Ni-MH battery still can work normally under low temperature (- 40 DEG C), and can have high power capacity, so as to not influence electronic product just Often running.
Invention content
In view of the above problems, the present invention provides a kind of low-temperature electrolyte of Ni-MH battery, aoxidized in a concentration of 8-11mol/L Soluble calcium salt, non-ionic surface active are added in the alkaline electrolyte of the lithium hydroxide of potassium and a concentration of 0.1-2mol/L Agent, inorganic inhibitor make electrolyte nodeless mesh precipitation at -40 DEG C of Ni-MH battery, appropriate positive and negative pole material are coordinated to make electricity Pond is tested, and 80% rated capacity is still can reach in -40 DEG C of cryogenic conditions standard charge and discharges.
To achieve the above object, the present invention solves by the following technical programs：
A kind of low-temperature electrolyte of Ni-MH battery, including electrolyte and additive, the electrolyte include potassium hydroxide and Lithium hydroxide, the additive include soluble calcium salt, nonionic surfactant, inorganic inhibitor, the additive each group Concentration point in the electrolytic solution is respectively：Soluble calcium salt 0.1-1mol/L；Nonionic surfactant 0.05-0.15mol/L； Inorganic inhibitor 0.01-0.08mol/L.
Specifically, the soluble calcium salt is calcium chloride, calcium gluconate, calcium monohydrogen phosphate, calcium lactate, calcium sulfate, nitric acid One kind in calcium, calcium chlorate, Calcium perchlorate, calcium bicarbonate, calcium dihydrogen phosphate.
Specifically, the nonionic surfactant is high-carbon fatty alcohol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, alkane Base phenol polyethenoxy ether, polyacrylamide, monoethanolamine, diethanol amine, triethanolamine one or more of compositions.
Specifically, the no agent corrosion inhibiter is chromate, in molybdate, tungstates, vanadate, nitrite, borate One kind.
Specifically, a concentration of 8-11mol/L of the potassium hydroxide.
Specifically, a concentration of 0.1-2mol/L of the lithium hydroxide.
The beneficial effects of the invention are as follows：
First, in the alkaline electrolysis of the lithium hydroxide of a concentration of 8-11mol/L potassium oxides and a concentration of 0.1-2mol/L Soluble calcium salt, nonionic surfactant, inorganic inhibitor are added in liquid, makes the electrolyte of the Ni-MH battery nothing at -40 DEG C Crystallization is precipitated, and appropriate positive and negative pole material is coordinated to make battery testing, 80% is still can reach in -40 DEG C of cryogenic conditions standard charge and discharges Rated capacity.
Second, during low temperature, the solubility of potassium hydroxide in water in alkaline electrolyte is very low, is easily saturated precipitation, adds Enter calcium ion, the concentration of soluble calcium salt is set as 0.1-1mol/L, the presence of calcium ion inhibits potassium hydroxide with crystal Form be precipitated, die down so as to avoid active substance, cell voltage caused to reduce, internal pressure raising, cause battery can not The problem of use.
Third, when the temperature is low, the surface tension of electrolyte are relatively large, are unfavorable for the formation of surface passivated membrane, from And the cycle life of battery can be influenced；Nonionic surfactant is added in, the surface tension of electrolyte is advantageously reduced, so as to change The wellability of kind electrolyte, the dispersibility for making electrolyte more preferably, are conducive to inhibit the formation of potassium hydroxide crystal.
4th, the positive and negative pole material of Ni-MH battery needs highly basic electrolyte, in cryogenic conditions to obtain high current density Under, the concentration of the electrolyte of strong basicity changes, and can accelerate meeting corroding electrode material, be easy to cause the damage of electrode material； Therefore, inorganic inhibitor is added in alkaline electrode solution, helps to reduce corrosion rate, improve electrode utilization rate.
Specific embodiment
In order to further appreciate that the feature of the present invention, technological means and the specific purposes reached, function, tie below Closing specific embodiment, the present invention is described in further detail.
A kind of low-temperature electrolyte of Ni-MH battery, including electrolyte and additive, electrolyte includes potassium hydroxide and hydrogen-oxygen Change lithium, additive includes soluble calcium salt, nonionic surfactant, inorganic inhibitor, and additive each component is in the electrolytic solution Concentration be respectively：Soluble calcium salt 0.1-1mol/L；Nonionic surfactant 0.05-0.15mol/L；Inorganic inhibitor 0.01-0.08mol/L。
The solubility of potassium hydroxide in water in alkaline electrolyte is reduced with the reduction of temperature, when temperature declines When, potassium hydroxide is easily saturated and is precipitated in the form of crystal, calcium ion is added in, since the presence of calcium ion inhibits hydroxide Potassium is precipitated in the form of crystal, is died down so as to avoid active substance, and cell voltage is caused to reduce, and internal pressure raising causes The problem of battery can not use.
Further, soluble calcium salt used in the present invention for calcium chloride, calcium gluconate, calcium monohydrogen phosphate, calcium lactate, One kind in calcium sulfate, calcium nitrate, calcium chlorate, Calcium perchlorate, calcium bicarbonate, calcium dihydrogen phosphate.
On the other hand, the surface tension of electrolyte is reduced with temperature and is increased in Ni-MH battery, and surface tension is bigger, more not Conducive to the formation of positive and negative pole material surface passivated membrane, so as to which the cycle life of battery can be influenced；Add in nonionic surfactant, The surface tension of electrolyte is advantageously reduced, so as to improve the wellability of electrolyte, the dispersibility for making electrolyte more preferably, is conducive to Inhibit the formation of potassium hydroxide crystal.
Further, nonionic surfactant used in the present invention is high-carbon fatty alcohol polyoxyethylene ether, fatty alcohol Polyoxyethylene ether, alkyl phenol polyoxyethylene ether, polyacrylamide, monoethanolamine, diethanol amine, triethanolamine one or more Composition.
Under cryogenic conditions, the concentration of the electrolyte of strong basicity changes, and can accelerate meeting corroding electrode material, be easy to cause The damage of electrode material；Therefore, inorganic inhibitor is added in alkaline electrode solution, helps to reduce corrosion rate, improve electrode Utilization rate.
Further, no agent corrosion inhibiter used in the present invention is chromate, molybdate, tungstates, vanadate, nitrous acid One kind in salt, borate.
Further, the positive and negative pole material of Ni-MH battery needs to prepare suitable electrolyte to obtain high current density Composition and ratio, a concentration of 8-11mol/L of potassium hydroxide used in the present invention, a concentration of 0.1-2mol/ of lithium hydroxide L, electrolyte composition and ratio can obtain higher current density.
Embodiment one：
Potassium hydroxide 8mol/L；Lithium hydroxide 0.1mol/L；Calcium chloride 0.1mol/L；High-carbon fatty alcohol polyoxyethylene ether 0.05mol/L；Chromate 0.01mol/L.
Embodiment two：
Potassium hydroxide 9mol/L；Lithium hydroxide 0.2mol/L；Calcium chloride 0.2mol/L；High-carbon fatty alcohol polyoxyethylene ether 0.07mol/L；Chromate 0.02mol/L.
Embodiment three：
Potassium hydroxide 10mol/L；Lithium hydroxide 0.3mol/L；Calcium chloride 0.4mol/L；High-carbon fatty alcohol polyoxyethylene ether 0.1mol/L；Chromate 0.04mol/L.
Example IV：
Potassium hydroxide 11mol/L；Lithium hydroxide 0.4mol/L；Calcium chloride 0.6mol/L；High-carbon fatty alcohol polyoxyethylene ether 0.12mol/L；Chromate 0.06mol/L.
Embodiment five：
Potassium hydroxide 8mol/L；Lithium hydroxide 2mol/L；Calcium chloride 1mol/L；High-carbon fatty alcohol polyoxyethylene ether 0.15mol/L；Chromate 0.08mol/L.
Embodiment six：
Potassium hydroxide 8mol/L；Lithium hydroxide 0.1mol/L；Calcium sulfate 0.1mol/L；Polyacrylamide 0.05mol/L；Tungsten Hydrochlorate 0.01mol/L.
Embodiment seven：
Potassium hydroxide 9mol/L；Lithium hydroxide 0.2mol/L；Calcium sulfate 0.2mol/L；Polyacrylamide 0.07mol/L；Tungsten Hydrochlorate 0.02mol/L.
Embodiment eight：
Potassium hydroxide 10mol/L；Lithium hydroxide 0.3mol/L；Calcium sulfate 0.4mol/L；Polyacrylamide 0.1mol/L；Tungsten Hydrochlorate 0.04mol/L.
Embodiment nine：
Potassium hydroxide 11mol/L；Lithium hydroxide 0.4mol/L；Calcium sulfate 0.6mol/L；Polyacrylamide 0.12mol/L； Tungstates 0.06mol/L.
Embodiment ten：
Potassium hydroxide 8mol/L；Lithium hydroxide 2mol/L；Calcium sulfate 1mol/L；Polyacrylamide 0.15mol/L；Tungstates 0.08mol/L。
Embodiment 11：
Potassium hydroxide 8mol/L；Lithium hydroxide 0.1mol/L；Calcium bicarbonate 0.1mol/L；Triethanolamine 0.05mol/L；Boron Hydrochlorate 0.01mol/L.
Embodiment 12：
Potassium hydroxide 9mol/L；Lithium hydroxide 0.2mol/L；Calcium bicarbonate 0.2mol/L；Triethanolamine 0.07mol/L；Boron Hydrochlorate 0.02mol/L.
Embodiment 13：
Potassium hydroxide 10mol/L；Lithium hydroxide 0.3mol/L；Calcium bicarbonate 0.4mol/L；Triethanolamine 0.1mol/L；Boron Hydrochlorate 0.04mol/L.
Embodiment 14：
Potassium hydroxide 11mol/L；Lithium hydroxide 0.4mol/L；Calcium bicarbonate 0.6mol/L；Triethanolamine 0.12mol/L； Borate 0.06mol/L.
Embodiment 15：
Potassium hydroxide 8mol/L；Lithium hydroxide 2mol/L；Calcium bicarbonate 1mol/L；Triethanolamine 0.15mol/L；Borate 0.08mol/L。
Comparative example one：
Potassium hydroxide 8mol/L；Lithium hydroxide 0.1mol/L.
(1) preparation of low-temperature electrolyte
Potassium hydroxide, lithium hydroxide, solubility calcium are added in deionized water according to the formula in embodiment and comparative example Salt, nonionic surfactant and inorganic inhibitor, are made into mixed solution.
(2) prepare positive and negative pole material, diaphragm and shell
Positive electrode：Matrix is copper facing nickel sheet, and active material is hickelous nydroxide, conductive agent is cobalt powder, additive is oxygen Change zinc, adhesive is polytetrafluoroethylene (PTFE)；
Negative material：Matrix is copper sheet, active material LaNi3.65Mg0.20Co1.00Al0.15, conductive agent for cobalt powder, addition Agent is zinc oxide, adhesive is polytetrafluoroethylene (PTFE)；
Diaphragm is PP materials.
Shell is copper shell.
(3) Ni-MH battery is made
According to conventional cell manufacturing method, negative material, diaphragm, positive electrode are wound into cylindric battery core, it will be electric Core is placed in copper shell, filling electrolyte, is completed the production after sealing.
(4) capacitance is tested
Under room temperature (25 DEG C) that the Sample Cell being fabricated to is fully charged, the capacitance under full power state is 100% at this time, Under different temperatures, the capacitance of test sample battery, the ratio of the capacitance under obtained capacitance and room temperature (25 DEG C) is holds Measure percentage.Temperature-capacitance parameter of section Example is measured, obtained capacity percentage data are as shown in table 1 below.
Capacity percentage under the different temperatures of 1 section Example of table and comparative example
As can be seen from Table 1, the discharge capacity percentage of comparative example one is reduced with the reduction of temperature, when temperature drops During to -40 DEG C, battery capacity is only the 55% of room temperature；And in embodiment five, when temperature drops to -40 DEG C, battery electricity Capacity is up to 80%, though other embodiments do not reach 80%, compared to comparative example one, the rated capacity of battery in low temperature Increase.
Embodiment described above only expresses 15 kinds of embodiments of the present invention, and description is more specific and detailed, but Can not the limitation to the scope of the claims of the present invention therefore be interpreted as.It should be pointed out that the ordinary skill people for this field For member, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the present invention's Protection domain.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.

Claims (6)

1. a kind of low-temperature electrolyte of Ni-MH battery, including electrolyte and additive, the electrolyte includes potassium hydroxide and hydrogen Lithia, which is characterized in that the additive includes soluble calcium salt, nonionic surfactant, inorganic inhibitor, described to add The concentration of agent each component in the electrolytic solution is added to be respectively：Soluble calcium salt 0.1-1mol/L；Nonionic surfactant 0.05- 0.15mol/L；Inorganic inhibitor 0.01-0.08mol/L.
2. the low-temperature electrolyte of a kind of Ni-MH battery according to claim 1, which is characterized in that the soluble calcium salt is Calcium chloride, calcium gluconate, calcium monohydrogen phosphate, calcium lactate, calcium sulfate, calcium nitrate, calcium chlorate, Calcium perchlorate, calcium bicarbonate, phosphoric acid One kind in calcium dihydrogen.
3. the low-temperature electrolyte of a kind of Ni-MH battery according to claim 1, which is characterized in that the non-ionic surface is lived Property agent for high-carbon fatty alcohol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, alkyl phenol polyoxyethylene ether, polyacrylamide, Dan Yi Hydramine, diethanol amine, triethanolamine one or more of compositions.
4. the low-temperature electrolyte of a kind of Ni-MH battery according to claim 1, which is characterized in that the no agent corrosion inhibiter is One kind in chromate, molybdate, tungstates, vanadate, nitrite, borate.
5. a kind of low-temperature electrolyte of Ni-MH battery according to claim 1, which is characterized in that the potassium hydroxide it is dense It spends for 8-11mol/L.
6. a kind of low-temperature electrolyte of Ni-MH battery according to claim 1, which is characterized in that the lithium hydroxide it is dense It spends for 0.1-2mol/L.
CN201711479562.9A 2017-12-29 2017-12-29 A kind of low-temperature electrolyte of Ni-MH battery Pending CN108232333A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111326794A (en) * 2018-12-17 2020-06-23 深圳先进技术研究院 Electrolyte, calcium ion secondary battery and preparation method thereof
CN111463499A (en) * 2020-03-18 2020-07-28 山东合泰新能源有限公司 Electrolyte for secondary zinc-nickel battery

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1313648A (en) * 2000-03-01 2001-09-19 三洋电机株式会社 Alkali secondary battery for stably working at wide range of temperature
CN1763995A (en) * 2005-08-30 2006-04-26 包头稀土研究院 Method for improving magnesium-based hydrogen-storage electrode capacity attenuation for nickel-hydrogen battery
CN101369672A (en) * 2008-10-07 2009-02-18 湖南科力远新能源股份有限公司 Special electrolytic solution for alkaline nickel-hydrogen battery
CN105390755A (en) * 2015-11-05 2016-03-09 衡阳电科电源有限公司 Super-wide-temperature-range nickel-hydrogen battery and manufacturing method therefor

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1313648A (en) * 2000-03-01 2001-09-19 三洋电机株式会社 Alkali secondary battery for stably working at wide range of temperature
CN1763995A (en) * 2005-08-30 2006-04-26 包头稀土研究院 Method for improving magnesium-based hydrogen-storage electrode capacity attenuation for nickel-hydrogen battery
CN101369672A (en) * 2008-10-07 2009-02-18 湖南科力远新能源股份有限公司 Special electrolytic solution for alkaline nickel-hydrogen battery
CN105390755A (en) * 2015-11-05 2016-03-09 衡阳电科电源有限公司 Super-wide-temperature-range nickel-hydrogen battery and manufacturing method therefor

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111326794A (en) * 2018-12-17 2020-06-23 深圳先进技术研究院 Electrolyte, calcium ion secondary battery and preparation method thereof
CN111326794B (en) * 2018-12-17 2021-07-20 深圳先进技术研究院 Electrolyte, calcium ion secondary battery and preparation method thereof
CN111463499A (en) * 2020-03-18 2020-07-28 山东合泰新能源有限公司 Electrolyte for secondary zinc-nickel battery
CN111463499B (en) * 2020-03-18 2021-12-28 山东合泰新能源有限公司 Electrolyte for secondary zinc-nickel battery

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