CN101262051B - A nickel-hydrogen high-temperature battery and its making method - Google Patents
A nickel-hydrogen high-temperature battery and its making method Download PDFInfo
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- CN101262051B CN101262051B CN2008100270503A CN200810027050A CN101262051B CN 101262051 B CN101262051 B CN 101262051B CN 2008100270503 A CN2008100270503 A CN 2008100270503A CN 200810027050 A CN200810027050 A CN 200810027050A CN 101262051 B CN101262051 B CN 101262051B
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Abstract
The invention provides a Ni-H high-temperature battery which comprises a positive electrode, a negative electrode, electrolyte and a battery separator, wherein, the positive electrode comprises an active substance, an adhesive and a binder; the active substance is one of oxide or hydroxide added with 1-5 percent of erbium, illinium or ytterbium by weight proportion or a plurality of special nickel hydroxides serving as adhesive; the adhesive (by weight percentage) is 5-8 percent of CoO and an oxide of 1-5 percent of erbium or illinium; the electrolyte comprises sodium hydroxide, lithium hydroxide and water, and 1-5 percent (by weight percentage) of boron compound is also added as the adhesive. The charge efficiency of the Ni-H high-temperature battery is greatly improved in high-temperature environment; the defect of existing Ni-H battery is improved and the charge efficiency of the battery is improved. The invention also provides a method for manufacturing the Ni-H high-temperature battery.
Description
Technical field
The present invention relates to the technical field of battery, particularly under hot conditions, still can keep Ni-MH battery than high recharge efficiency.
Background technology
Ni-MH battery is the substitute products of early stage nickel-cadmium cell, similar on Ni-MH battery and the nickel-cadmium cell profile, and the positive pole of Ni-MH battery and nickel-cadmium cell are also basic identical, all be to be anodal with the nickel hydroxide, what the main distinction was the employing of nickel-cadmium battery negative pole plate is the cadmium active material, and Ni-MH battery is to be negative pole with the high energy hydrogen-storage alloy, so Ni-MH battery has bigger energy.Simultaneously Ni-MH battery is also similar substantially to nickel-cadmium cell aspect electrochemical properties, thus Ni-MH battery replacement nickel cadmium cell fully in use, and do not need equipment is carried out any transformation.It is the battery of at present environmental protection, does not re-use poisonous cadmium, can eliminate the pollution problem that heavy metal element brings environment.Ni-MH battery has bigger energy density ratio, this means to use Ni-MH battery can prolong the operating time of equipment effectively not for digital equipment increases under the situation of additional weight.Simultaneously Ni-MH battery is also similar substantially to nickel-cadmium cell aspect electrology characteristic, fully can the replacement nickel cadmium cell when practical application, and do not need equipment is carried out any transformation.Another advantage of Ni-MH battery is: reduced to exist in the nickel-cadmium cell " memory effect " greatly, this can use Ni-MH battery more easily.
At present, an important use of Ni-MH battery is to be applied in the field of power tools, because wireless chargeable electric tool fast development in recent years brings great convenience to people.In the prior art, Ni-MH battery product subject matter in actual applications is that capacity, the charging and discharging capabilities temperature influence of battery is very big, descends to some extent with the electrical property of temperature rising battery.And electric tool in use requires big flow discharge, in addition, also requires Ni-MH battery should have big flow charge function in order to shorten the charging interval, raises and inevitably will produce battery temperature in the large current density electric process, reaches more than 45 ℃.Current people are making great efforts to develop the rechargeable nickel-hydrogen battery of used for electric vehicle, and are more harsher with the battery performance demands than other electric tool, and bigger charging and discharging currents be arranged, and the temperature of use is higher.
In addition, in stand-by power supply fields such as solar energy utilization and emergency lighting, battery is through being everlasting more than 45 ℃ under the hot environment, with the little electric current of about 0.05C charge for a long time (that is: high temperature, low range charging).Ni-MH battery uses under high ambient conditions needs to guarantee higher charge efficiency and overcharging resisting ability, and existing conventional Ni-MH battery does not reach instructions for use.
When Ni-MH battery was in hot environment, the overpotential of its anodal oxygen reaction of formation (oxygen deposition potential) reduced, and caused anodal charge efficiency to reduce; Simultaneously, because the equalizing pressure of hydrogen bearing alloy increases, and the hydrogen of hydrogen bearing alloy also reduces,, make hydrogen pass barrier film and enter positive pole in the negative pole, quickened anodal capacity and reduced so the hydrogen dividing potential drop in the battery increases.The performance of entire cell and the performance of each parts are all closely bound up.For improving the high temperature serviceability of entire cell, can improve the high temperature serviceability of nickel hydroxide positive plate (as ZL99116113.0), hydrogen storage alloy negative or alkaline electrolyte (as ZL00108386.4) respectively.ZL99116113.0 is by adding the high-temperature charging efficient of improving Ni-MH battery with respect to the titanium elements additive of the 0.1%-15% of nickel hydroxide weight in nickel hydroxide positive plate, but its temperature that is suitable for is also only about 50 ℃.ZL00108386.4 adds wolframic acid ion and sodium ion in electrolyte, the W elements that exists with the wolframic acid ion is absorbed by positive pole, form film electrochemical stability, that cover positive electrode active material powder, sodium ion is in the battery charging and discharging circulation, the lattice of penetrable positive active material, make lattice generation strain, with the charge efficiency of raising battery under hot environment, but its temperature that is suitable for also only can reach about 50 ℃.
Summary of the invention
The object of the present invention is to provide the higher nickel-hydrogen high-temperature battery of a kind of charge efficiency at high temperature.
Another object of the present invention provides the manufacture method of described nickel-hydrogen high-temperature battery.
For achieving the above object, solution of the present invention is:
A kind of nickel-hydrogen high-temperature battery comprises positive pole, negative pole, electrolyte and battery diaphragm;
Described positive pole comprises active material, additive, binding agent; Described active material is to have added the oxide of erbium, yttrium or ytterbium element that weight ratio is 1%-5% or wherein one or more the special nickel hydroxide of hydroxide; Described additive be weight percentage for the CoO of 5%-8% and percentage by weight be the erbium of 1%-5% or the oxide of yttrium;
Described electrolyte comprises NaOH, lithium hydroxide, water, and the boron compound that also adds percentage by weight and be 1%-5% is as additive.
Described binding agent is that concentration expressed in percentage by weight is 60% polytetrafluoroethylsolution solution, and 2%-3% by weight percentage adds.
Described binding agent comprises sodium carboxymethylcellulose, and 0.1%-0.5% by weight percentage adds.
The manufacture method of described nickel-hydrogen high-temperature battery may further comprise the steps:
The first step, use and added the erbium of weight ratio as 1%-5%, the oxide of yttrium or ytterbium element or hydroxide wherein one or more as the special nickel hydroxide of additive positive active material as battery, the oxide that adds erbium that CoO that percentage by weight is 5%-8% and percentage by weight be 1%-5% or yttrium again is as additive, PTFE (polytetrafluoroethylene) solution (60% concentration) that adds weight ratio and be 2%-3% adds CMC that weight ratio is 0.1%-0.5% (sodium carboxymethylcellulose) and the water of weight ratio 15%-30% again and stirs into anode sizing agent as binding agent;
Second step was coated to anode sizing agent on the anodal matrix, passed through oven dry, roll-in and cut operation and make battery positive plate;
The 3rd step stacked gradually the formation electrode group of reeling with positive plate, diaphragm paper, negative plate, and electrode is assembled in the battery steel shell;
The 4th step, inject electrolyte, the enclosed cell housing changes into through overcharging and promptly to produce nickel-hydrogen high-temperature battery.
After adopting such scheme, nickel-hydrogen high-temperature battery provided by the invention since added the oxide of Er (erbium), Y (yttrium), Yb elements such as (ytterbiums) in the positive pole or hydroxide as additive, and used and added the electrolyte of the compound of boron as additive, under hot environment, can improve the oxygen deposition potential of anode, thereby improve the high-temperature charging efficient of battery.
Subordinate list 1 is nickel-hydrogen high-temperature battery provided by the invention and the comparison of charge efficiency at high temperature of existing Ni-MH battery.
Subordinate list 1
| Different temperatures environment charge efficiency | 45℃ | 55℃ | 65℃ | 70℃ | 75℃ |
| Existing Ni-MH battery | ≈80％ | ≈60％ | ≈50％ | ≈40％ | ≈30％ |
| Battery provided by the invention | ＞95％ | ＞90％ | ＞85％ | ＞75％ | ＞70％ |
The present invention is similar to existing nickel-hydrogen battery structure, but the charge efficiency of the present invention under hot environment improve a lot, and has improved the shortcoming of existing Ni-MH battery, has improved the charge efficiency of battery.
Description of drawings
Fig. 1 is the cutaway view of nickel-hydrogen high-temperature battery of the present invention.
Embodiment
The nickel-hydrogen high-temperature battery that the process in detail that gives an actual example is below made is lifted the fact that comparative example proves that the charge efficiency of nickel-hydrogen high-temperature battery under hot environment in this example is improved simultaneously, but is not intended to limit the scope of the invention.
For convenient the differentiation described, the special nickel hydroxide that this method is used, add oxide that weight ratio is 1%-5%Er (erbium), Y (yttrium), Yb elements such as (ytterbiums) or hydroxide as additive by mechanical mixing at this nickel hydroxide, all used " special nickel hydroxide " expression hereinafter.The nickel hydroxide that general battery uses does not wherein have the oxide of Er (erbium), Y (yttrium), Yb (ytterbium) element of etc.ing or hydroxide as additive, represents with " ordinary hydrogen nickel oxide ".The addition of positive active material and binding agent is with conventional interpolation scope of the prior art among the present invention.
Embodiment 1
With special nickel hydroxide, cobalt oxide (CoO), erbium oxide (Er
2O
3) mix by 100: 8: 4 part by weight, PTFE (polytetrafluoroethylene) solution (60% concentration) that adds percentage by weight and be 2%-3% is as binding agent, the water that adds CMC that percentage by weight is 0.1%-0.5% (sodium carboxymethylcellulose) and percentage by weight 15%-30% again stirs into anode sizing agent and stirs, evenly be coated on the matrix made of foaming nickel, through oven dry, roll-in, operation such as cut, make positive plate (because the manufacture method of battery positive plate is a known technology, and non-emphasis of the present invention, so will not describe in detail in the literary composition).
Hydrogen storing alloy powder, acetylene black, nickel powder are mixed by 100: 0.5: 0.5 part by weight, SBR (butadiene-styrene rubber) solution (50% concentration) that add to add weight ratio and be 1%-3% is as binding agent, the water that adds HPMC that weight ratio is 0.1%-0.5% and weight ratio 15%-30% again stirs into anode sizing agent and stirs, evenly be coated on the nickel plated steel strip, through oven dry, roll-in, operation such as cut, make negative plate (because the manufacture method of cell negative plate is a known technology, and non-emphasis of the present invention, so will not describe in detail in the literary composition).
In concentration is that to add concentration in 25% the NaOH aqueous solution be that 2% LiOH and concentration are 3% kodalk (NaBO
2), stir, promptly can be made into the electrolyte that this method is used after the cooling.
Referring to Fig. 1, the battery diaphragm 3 that positive plate 1, negative plate 2 and polypropylene material are made stacks gradually to reel and constitutes the electrode group, and electrode is assembled in the battery steel shell 4, injects electrolyte, and the enclosed cell housing changes into through overcharging and promptly to produce nickel-hydrogen high-temperature battery.
Comparative example 1
In comparative example 1, do not add boron compound as additive when making electrolyte, other all identical with example of making 1 method is produced the nickel-hydrogen high-temperature battery of comparative example 1.
Comparative example 2
In comparative example 2, do not add erbium oxide (Er when making positive plate
2O
3) as additive.Other all identical with example of making 1 method is produced the nickel-hydrogen high-temperature battery of comparative example 2.
Comparative example 3
In comparative example 3, do not add erbium oxide (Er when making positive plate
2O
3) as additive.Do not add boron compound as additive when making electrolyte.Other all identical with example of making 1 method is produced the nickel-hydrogen high-temperature battery of comparative example 3.
Comparative example 4
In comparative example 4, the nickel hydroxide that the making positive plate uses is the ordinary hydrogen nickel oxide.Do not add boron compound as additive when making electrolyte.Other all identical with example of making 1 method is produced the nickel-hydrogen high-temperature battery of comparative example 4.
Then, the battery of making embodiment 1 and comparative example 1-4 making was charged 14 hours with 180mA, discharge into 1.0V, circulate 3 times with 360mA, thus the nickel-hydrogen high-temperature battery that activation embodiment 1 and comparative example 1-4 make.
The battery examples that activated is tested respectively, and test result is got its mean value.
The charge efficiency method of investigating under the battery different temperatures is: each example and comparative example battery are carried out 0.05C multiplying power charging 24 hours respectively under 45 ℃, 55 ℃, 65 ℃, 70 ℃, 75 ℃ environment, with the 0.25C multiplying power discharging to 1.0V, the counting cell discharge capacity, and with this battery normal temperature under the battery actual capacity relatively, thereby investigate its charge efficiency under hot environment.Generally the ratio of discharge capacity of the cell under the hot environment and this battery discharge capacity is at normal temperatures represented with percentage.
Embodiment 1 and each comparative example charge efficiency at high temperature are shown in subordinate list 2:
| The special nickel hydroxide of positive pole | The anodal erbium oxide that adds | Electrolyte adds boron compound | 45 ℃ of charge efficiencies | 55 ℃ of charge efficiencies | 65 ℃ of charge efficiencies | 70 ℃ of charge efficiencies | 75 ℃ of charge efficiencies | |
| Embodiment 1 | Be | Be | Be | 99％ | 95％ | 89％ | 77％ | 73％ |
| Comparative example 1 | Be | Be | Not | 90％ | 82％ | 68％ | 60％ | 55％ |
| Comparative example 2 | Be | Not | Be | 90％ | 85％ | 70％ | 65％ | 60％ |
| Comparative example 3 | Be | Not | Not | 80％ | 65％ | 57％ | 50％ | 45％ |
| Comparative example 4 | Not | Not | Not | 78％ | 62％ | 55％ | 42％ | 35％ |
By last diagram, compare with the battery of the comparative example 4 that uses the ordinary hydrogen nickel oxide, used the charge efficiency of comparative example 3 batteries under each temperature environment of special nickel hydroxide to increase.
Compare with comparative example 3 batteries that only use special nickel hydroxide, use special nickel hydroxide and added comparative example 2 batteries of boron compound as additive in electrolyte, its charge efficiency under each temperature environment is further enhanced.
Compare with comparative example 3 batteries that only use special nickel hydroxide, use special nickel hydroxide and in positive pole, added erbium oxide (Er
2O
3) as additive, but in electrolyte, do not add comparative example 1 battery of boron compound as additive, its charge efficiency under each temperature environment is further enhanced, and is comparatively approaching with the battery performance of comparative example 2.
But use special nickel hydroxide, and in positive pole, added erbium oxide (Er
2O
3) as additive, in electrolyte, add example of making 1 battery of boron compound as additive, with the battery of above comparative example 1,2,3,4, its charge efficiency under each temperature environment obtains maximum raising.
Secondly, the anodal consumption of erbium oxide that adds is through experimental verification in above-mentioned example, very few as addition, the effect of the battery high-temperature charging efficient that can not be fully improved, on the contrary, too much as addition, then the ratio of nickel hydroxide descends in the positive pole, capacity descends under the unit mass, so the additive addition is relative and nickel hydroxide 1%-5% (wt%) preferably.
In addition, the consumption that electrolyte adds boron compound in above-mentioned example is through experimental verification, and is very few as addition, and the effect of the battery high-temperature charging efficient that can not be fully improved is too much as addition on the contrary, then [OH in the electrolyte
-] ratio descend, battery capacity reduces, so the additive addition is the 1-5% (wt%) of electrolyte total amount preferably.
What represent in above-mentioned example is to add erbium oxide (Er in positive pole
2O
3) as the situation of additive, but be to use under the situation of the oxide that is selected from least a element in erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), the yttrium (Y) or hydroxide, also can obtain same effect.
In sum, use the nickel-hydrogen high-temperature battery of this method manufacturing since added the oxide of Er (erbium), Y (yttrium), Yb elements such as (ytterbiums) in the positive pole or hydroxide as additive, and used and added the electrolyte of the compound of boron as additive, under hot environment, can improve the oxygen deposition potential of anode, improved the high-temperature charging efficient of battery, make the present invention under 75 ℃ high temperature, charge efficiency still can reach more than 70%.
Claims (4)
1. a nickel-hydrogen high-temperature battery comprises positive pole, negative pole, electrolyte and battery diaphragm; It is characterized in that:
Described positive pole comprises active material, additive, binding agent; Described active material is that having added with respect to the nickel hydroxide percentage by weight is the oxide of erbium, yttrium or ytterbium element of 1%-5% or wherein one or more the special nickel hydroxide of hydroxide; Described additive is for being the cobalt oxide CoO of 5%-8% with respect to the nickel hydroxide percentage by weight and being the erbium of 1%-5% or the oxide of yttrium with respect to the nickel hydroxide percentage by weight;
Described electrolyte comprises NaOH, lithium hydroxide, water, and the boron compound that also adds percentage by weight and be 1%-5% is as additive.
2. nickel-hydrogen high-temperature battery as claimed in claim 1 is characterized in that: described binding agent is that concentration expressed in percentage by weight is 60% polytetrafluoroethylsolution solution, adds by the 2%-3% with respect to the nickel hydroxide percentage by weight.
3. nickel-hydrogen high-temperature battery as claimed in claim 1 or 2 is characterized in that: described binding agent comprises sodium carboxymethylcellulose, adds by the 0.1%-0.5% with respect to the nickel hydroxide percentage by weight.
4. the manufacture method of nickel-hydrogen high-temperature battery according to claim 1 may further comprise the steps:
The first step, use and added with respect to the erbium of nickel hydroxide percentage by weight as 1%-5%, the oxide of yttrium or ytterbium element or hydroxide wherein one or more as the special nickel hydroxide of additive positive active material as battery, add again with respect to the nickel hydroxide percentage by weight and be the cobalt oxide CoO of 5%-8% and be that the oxide of the erbium of 1%-5% or yttrium is as additive with respect to the nickel hydroxide percentage by weight, adding with respect to the nickel hydroxide percentage by weight be the concentration expressed in percentage by weight of 2%-3% be 60% polytetrafluoroethylsolution solution as binding agent, add again with respect to the nickel hydroxide percentage by weight and be the sodium carboxymethylcellulose of 0.1%-0.5% and stir into anode sizing agent with respect to the water of nickel hydroxide percentage by weight 15%-30%;
Second step was coated to anode sizing agent on the anodal matrix, passed through oven dry, roll-in and cut operation and make battery positive plate;
The 3rd step stacked gradually the formation electrode group of reeling with positive plate, diaphragm paper, negative plate, and electrode is assembled in the battery steel shell;
The 4th step, inject electrolyte, the enclosed cell housing changes into through overcharging and promptly to produce nickel-hydrogen high-temperature battery.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100270503A CN101262051B (en) | 2008-03-27 | 2008-03-27 | A nickel-hydrogen high-temperature battery and its making method |
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|---|---|---|---|
| CN2008100270503A CN101262051B (en) | 2008-03-27 | 2008-03-27 | A nickel-hydrogen high-temperature battery and its making method |
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| CN101262051A CN101262051A (en) | 2008-09-10 |
| CN101262051B true CN101262051B (en) | 2010-07-28 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102956892B (en) * | 2012-11-01 | 2015-04-22 | 浙江天能能源科技有限公司 | High temperature nickel-hydrogen battery and preparation method thereof |
| CN103794798B (en) * | 2014-01-27 | 2016-04-20 | 中南大学 | A kind of battery cathode slurry and preparation method |
| CN106340682A (en) * | 2016-10-31 | 2017-01-18 | 河南创力新能源科技股份有限公司 | Nickel-metal hydride battery electrolyte additive, electrolyte containing additive and nickel-metal hydride battery |
| CN108682902B (en) * | 2018-06-01 | 2020-06-09 | 河南省恒明新能源有限公司 | Large-capacity square nickel-hydrogen battery |
| CN108711642B (en) * | 2018-06-01 | 2020-06-09 | 河南省恒明新能源有限公司 | Single-bag type high-power long-life nickel-hydrogen battery |
| CN108682901B (en) * | 2018-06-01 | 2020-05-19 | 河南省恒明新能源有限公司 | High-capacity double-bag type iron-nickel battery |
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Denomination of invention: A nickel-hydrogen high-temperature battery and its making method Effective date of registration: 20170712 Granted publication date: 20100728 Pledgee: Dongguan rural commercial bank Limited by Share Ltd. Songshan Lake Science and Technology Branch Pledgor: DONGGUAN MCNAIR TECHNOLOGY Co.,Ltd.|DONGGUAN MCNAIR NEW POWER Co.,Ltd.|TECHNICAL INSTITUTE OF LITHIUM BATTERY ENERGY-SAVING TECHNOLOGY OF MCNAIR, DONGGUAN. Registration number: 2017990000356 |
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