CN1320681C - Long time stored nickel-hydrogen battery and mfg. method thereof - Google Patents

Abstract

The invention discloses a hydrogen-nickel battery that can be stored for a long time. The active material of the positive plate is Ni(OH) ₂ coated with β-CoOOH, the diaphragm is a non-woven cloth diaphragm that has undergone sulfonation treatment, and the electrolyte contains soluble Alkaline electrolyte of bromide R _n Br _m . The invention also discloses a method for making the nickel-hydrogen battery, including making the positive and negative electrodes, assembling the battery, and forming the battery. The positive electrode is prepared by first preparing Ni(OH) ₂ coated with β-CoOOH, and then It is made by adding a binder with the current collector as the skeleton. The hydrogen-nickel battery of the present invention surpasses the existing nickel-hydrogen battery in terms of capacity, internal resistance and cycle life performance, and its most notable feature is that the battery has excellent storability, good over-discharge resistance performance and charge retention capacity. Stored at room temperature 20±5°C for one year, the battery voltage is still above 1.2V, and the capacity recovery rate reaches 100%; after a long-term short circuit at a temperature of 45°C, the battery capacity has almost no loss; in addition, the battery charge retention The capacity is 5% to 10% higher than that of ordinary nickel-hydrogen batteries.

Description

A kind of long-term storage nickel-hydrogen battery and its manufacturing method

technical field

The invention relates to a battery used for directly converting chemical energy into electric energy, depositing active materials on a carrier by an electrochemical method to manufacture a nickel hydroxide electrode of an alkaline storage battery, in particular to a nickel-hydrogen battery capable of long-term storage and a manufacturing method thereof.

Background technique

Nickel-hydrogen battery is a new generation of high-energy alkaline secondary battery after nickel-cadmium battery. It has the characteristics of high capacity, high power, and no pollution. It is one of the important development directions of secondary batteries today. However, because the positive and negative electrode materials used are different from those of nickel-cadmium batteries, the mechanism of electrochemical reaction is also different. Compared with nickel-cadmium batteries, nickel-hydrogen batteries have poor long-term storage performance, and their self-discharge is significantly greater than that of nickel-cadmium batteries. During the long-term storage process, the hydrogen in the hydrogen electrode in the hydrogen-nickel battery is easy to escape from the hydrogen storage alloy to form hydrogen gas. After the hydrogen gas migrates to the surface of the positive electrode, it reduces the conductive layer coated on the surface of NiOOH, making the already The formation of the conductive network is reduced, causing a reduction in electricity. At the same time, the conductive network is irreversibly damaged, causing the capacity loss of the Ni-MH battery. The positive electrode active material of the existing nickel-hydrogen battery is generally made by mixing common nickel hydroxide Ni(OH) ₂ with conductive agents such as cobalt powder and cobaltous oxide, and the positive electrode is based on foamed nickel. Cobaltous oxide is currently the best conductive agent. It will gradually dissolve and precipitate in alkaline electrolyte to form Ni(OH) ₂ with β-Co(OH) ₂ coating layer, and then charge and oxidize on Ni( OH) ₂ forms a coating layer of cobalt oxyhydroxide β-CoOOH, but during the oxidation process, most of β-Co(OH) ₂ is converted into β-CoOOH, and a small part is converted into Co(OH) ₃ , Due to the uneven current density at each point inside the battery, the thickness and density of the β-CoOOH coating layer are also different, resulting in uneven distribution of the conductive network, and the anti-reduction ability of Co(OH) ₃ is not as good as that of β-CoOOH. During the long-term storage process, Co(OH) ₃ is continuously reduced to β-Co(OH) ₂ , which will also cause the power to decrease, cause the conductive network to be destroyed, and reduce the recoverable capacity ratio of the battery.

Contents of the invention

The technical problem to be solved by the present invention is to overcome the defects of the prior art and propose a nickel-hydrogen battery that can be stored for a long time with high charge retention capability, good over-discharge resistance and capacity loss.

Another technical problem to be solved by the present invention is to overcome the defects of the prior art and propose a method for manufacturing a nickel-hydrogen battery that can be stored for a long time.

For the nickel-hydrogen battery that can store for a long time of the present invention, above-mentioned technical problem is solved like this:

This nickel-hydrogen battery which can be stored for a long time includes a positive electrode sheet, a negative electrode sheet, a diaphragm between the positive and negative electrode sheets, a casing and an electrolyte injected into the casing.

The characteristics of this long-term storage nickel-hydrogen battery are:

The active material of the positive plate is nickel hydroxide Ni(OH) ₂ coated with cobalt oxyhydroxide β-CoOOH. Ni(OH) ₂ coated with cobalt oxyhydroxide (β-CoOOH) is used as the active material of the positive electrode sheet, and no other conductive agent is added to make a nickel-hydrogen battery. This battery improves the charge retention capacity. During storage, Ni The β-CoOOH conductive network of the coating layer on the (OH) ₂ surface will not be destroyed, and has the characteristics of long-term storage, no loss of battery capacity, and good over-discharge resistance.

For the nickel-hydrogen battery that can be stored for a long time of the present invention, the above-mentioned technical problems can be preferably solved like this:

The diaphragm is a sulfonated non-woven cloth diaphragm to achieve the effect of long-term storage. Sulfonation treatment is a kind of hydrophilic treatment. The diaphragm after sulfonation treatment has the advantages of good hydrophilicity and small self-discharge. The good hydrophilicity of the diaphragm is conducive to the maintenance of the electrolyte of the diaphragm during long-term storage or working process of the battery. rate, which is conducive to maintaining the utilization rate of the active material. During the storage or working process of the nickel-hydrogen battery, the impurity NH ₂ -ions in the separator will react with Ni(OH) ₂ , resulting in the failure of the reacted Ni(OH) ₂ . It causes the battery to reduce the recoverable capacity ratio, and the impurity NH ₂ -ion content in the sulfonated separator is lower than that of the separator using other treatment methods, which is beneficial to improve the self-discharge performance of the battery.

The electrolyte is an alkaline electrolyte containing soluble bromide R _n Br _m to improve the long-term storage performance and cycle performance of the battery. Bromide ions can effectively prevent the hydrogen storage alloy powder from being over-oxidized and protect the hydrogen storage capacity of the hydrogen storage alloy powder.

For the nickel-hydrogen battery that can be stored for a long time of the present invention, the above-mentioned technical problem can be further solved like this:

The sulfonation treatment is fuming sulfuric acid treatment, chlorosulfonic acid treatment, or anhydrous sulfuric acid treatment.

The non-woven fabric is a non-woven fabric made of polyolefin fibers.

The polyolefin fibers are polypropylene fibers or polyethylene fibers.

The soluble bromide R _n Br _m contained in the electrolyte solution is KBr, NaBr, NiBr ₂ , or CoBr ₂ .

The electrolytic solution is an aqueous solution whose molar ratio is KOH:LiOH:NaOH:R _n Br _m =(5-8):(0.1-1.0):(0.1-3.0):(0.001-0.100).

For the manufacture method of the nickel-hydrogen battery that can store for a long time of the present invention, above-mentioned technical problem is solved like this:

The manufacturing method of this nickel-hydrogen battery that can be stored for a long time is characterized in that the following steps are arranged successively:

(1) Making positive and negative electrodes:

First prepare Ni(OH) ₂ coated with β-CoOOH, and then use the Ni(OH) ₂ coated with β-CoOOH to make a positive electrode sheet with the current collector as the skeleton and add a binder;

Use the current collector as the skeleton and add a binder to make the negative electrode sheet;

(2) Assembling the battery: After the formed positive and negative electrodes and the diaphragm are matched and put into the battery case, the electrolyte is injected and sealed;

(3) Battery formation: aging the sealed battery for a set time at a set temperature.

For the manufacture method of the nickel-hydrogen battery that can be stored for a long time of the present invention, the above-mentioned technical problems can be preferably solved like this:

Said preparation of Ni(OH) coated with β-CoOOH has _the following steps in turn:

(1) At a temperature of 45°C to 50°C, according to the molar ratio of Ni:Co:Zn=1:(0.02～0.05):(0.04～0.08), the concentration of 2.8mol/L～3.0mol/L Nickel sulfate aqueous solution, zinc sulfate aqueous solution with a concentration of 2.8mol/L～3.0mol/L and cobalt sulfate aqueous solution with a concentration of 2.8mol/L～3.0mol/L were respectively injected into the reactor and mixed, and then gradually added dropwise with a concentration of 3mol/L～ 5mol/L sodium hydroxide aqueous solution, stabilize the pH value to 13-14, and crystallize nickel, zinc and cobalt ions under constant stirring;

(2) Add the cobalt sulfate aqueous solution of concentration 2.8mol/L～3.0mol/L in the reactor gradually, the cobalt add-on is 4.6%～5.4% of the molar weight of nickel, the pH value is stabilized to 9～10, makes cobalt Ionic crystallization covers the surface of Ni(OH) ₂ , and then washes the hydroxide several times with deionized water to change the pH value to 7-8, then dehydrates and dries to obtain a coating layer of β-Co(OH) ₂ Zinc-added Ni(OH) ₂ ;

(3) Add the NaOH aqueous solution with a concentration of 68wt～72wt% dropwise to the above-mentioned zinc-added Ni(OH) ₂ coated with β-Co(OH) ₂ , after the complete contact reaction occurs between the two under constant stirring, The amount of NaOH aqueous solution is 8% to 12% of the weight of the zinc-added Ni(OH) ₂ of the β-Co(OH) ₂ cladding layer prepared above, and heat baked at a temperature of 90°C to 110°C for 1.2 hours ~1.8 hours, oxidize the β-Co(OH) ₂ coating layer to β-CoOOH coating layer, finally wash with deionized water and adjust the pH value to 7~8, then dehydrate and dry to obtain the coated β-CoOOH coating layer Ni(OH) ₂ of CoOOH.

The assembly of the battery is to put the positive and negative electrodes and the diaphragm into the battery case, inject the electrolyte and seal it to obtain a hydrogen-nickel battery. The electrolyte is an alkaline solution containing soluble bromide R _n Br _m Electrolyte to improve the long-term storage performance and cycle performance of the battery.

The formation of the battery is to age the sealed battery at a set temperature for 1 to 10 days.

The separator is a sulfonated non-woven fabric separator. In order to achieve the effect of long-term storage.

For the manufacture method of the nickel-hydrogen battery that can store for a long time of the present invention, above-mentioned technical problem can be further solved like this:

The sulfonation treatment is fuming sulfuric acid treatment, chlorosulfonic acid treatment, or anhydrous sulfuric acid treatment.

The non-woven fabric is a non-woven fabric made of polyolefin fibers.

The polyolefin fibers are polypropylene fibers or polyethylene fibers.

The electrolytic solution is an aqueous solution whose molar ratio is KOH:LiOH:NaOH:R _n Br _m =(5-8):(0.1-1.0):(0.1-3.0):(0.001-0.100).

The binder is a combination of polytetrafluoroethylene PTFE aqueous solution, hydroxymethylcellulose CMC aqueous solution, hydroxypropylmethylcellulose HPMC aqueous solution, polyvinyl alcohol PVAL aqueous solution, sodium polyacrylate PAAS aqueous solution, and styrene-butadiene rubber SBR aqueous solution. species or a mixture of any two or more species.

The invention adopts the Ni-MH battery made of Ni(OH) ₂ coated with β-CoOOH, and has good comprehensive performance. In addition to capacity, internal resistance, and cycle life performance exceeding that of the existing nickel-hydrogen batteries, its most notable feature is that the battery has excellent storage properties, good over-discharge resistance and charge retention. Stored at room temperature 20±5°C for one year, the battery voltage is still above 1.2V, and the capacity recovery rate reaches 100%; after a long-term short-circuit at a temperature of 45°C, the battery capacity has almost no loss; in addition, the battery charge retention The capacity is 5% to 10% higher than that of general nickel-hydrogen batteries.

Detailed ways

A AA-type nickel-hydrogen battery with a capacity of 2000mAh that can be stored for a long time, including a negative electrode that is filled with dry powder using copper mesh as the skeleton, soaked in the binder for a while after rolling, dried, and cut into shape. , The negative electrode sheet and the non-woven fabric separator made of sulfonated polypropylene fiber are rolled into a cylindrical shape and loaded into the battery case, and then filled with electrolyte and sealed. The active material of the positive electrode sheet is coated with β-CoOOH Ni(OH) ₂ .

The manufacturing method of this nickel-hydrogen battery which can be stored for a long time includes making positive and negative electrodes, assembling the battery and forming the battery.

The production of the positive electrode sheet is to first prepare Ni(OH) ₂ coated with β-CoOOH, and take the following steps in sequence:

At a temperature of 48°C, according to the molar ratio of Ni: Co: Zn=1: 0.04: 0.06, the nickel sulfate aqueous solution with a concentration of 2.9mol/L, the zinc sulfate aqueous solution with a concentration of 2.9mol/L and the zinc sulfate aqueous solution with a concentration of 2.9mol/L The cobalt sulfate aqueous solution was poured into the reaction kettle and mixed, and then the sodium hydroxide aqueous solution with a concentration of 4mol/L was gradually added dropwise to stabilize the pH value to 13-14, and nickel, zinc, and cobalt ions were all crystallized under constant stirring;

Then gradually add an aqueous solution of cobalt sulfate with a concentration of 2.9 mol/L into the reaction kettle, the amount of cobalt added is 5.0% of the molar amount of nickel, and the pH value is stabilized to 9-10, so that the cobalt ion crystallizes and coats the surface of Ni(OH) ₂ , and then wash the hydroxide multiple times with deionized water to change the pH value to 7-8, then dehydrate and dry to obtain zinc-added Ni(OH) ₂ with a β-Co(OH) ₂ coating layer;

Concentration is that the NaOH aqueous solution of 70wt% is added dropwise to the above-mentioned zinc-added Ni(OH) with β-Co(OH) ₂ cladding layer In ₂ , after the two fully contacted and reacted under constant stirring, make the consumption of NaOH aqueous solution It is 10% of the weight of the zinc-added Ni(OH) of the β-Co( _OH ) coating _layer prepared above, and it is baked at a temperature of 100° C. for 1.5 hours to make the β-Co(OH) _coating The layer is oxidized to form a coating layer of β-CoOOH, and finally washed with deionized water to adjust the pH value to 7-8, then dehydrated and dried to obtain Ni(OH) ₂ coated with β-CoOOH.

Then use Ni(OH) ₂ coated with β-CoOOH, and use the foamed nickel current collector as the skeleton to carry out dry powder intercalation. After rolling into a pole piece, soak it in polytetrafluoroethylene PTFE aqueous solution for a while and then dry it. Cut into positive sheets.

The production of the negative electrode sheet is to use the copper mesh current collector as the skeleton to carry out dry powder filling, roll to form the electrode sheet, soak in the polytetrafluoroethylene PTFE aqueous solution for a while, then dry it, and finally cut it into the negative electrode sheet.

The assembly of the battery is to roll the positive and negative electrode sheets and the diaphragm into a cylindrical shape, put them into the battery case, inject the electrolyte solution, and seal it to obtain a hydrogen-nickel battery. It is an aqueous solution of KOH:LiOH:NaOH:KBr=6:0.5:2:0.05.

The formation of the battery is to age the sealed battery at a temperature of 45° C. for 24 hours.

And with existing Ni (OH) ₂ making capacity is the method for the common AA type nickel-hydrogen battery of 2000mAh, and its positive plate is made that the positive electrode active material adopts common nickel hydroxide that adds zinc, takes foamy nickel as skeleton, adds 5wt% Cobaltous oxide, using dry powder embedding method, and then rolled into a pole piece, soaked in polytetrafluoroethylene PTFE aqueous solution and then dried into a positive pole piece. The manufacture of the negative electrode sheet and the assembly of the battery are the same as the specific embodiment of the present invention, but the separator used is a non-woven fabric made of fluorinated polypropylene fiber, and the battery is formed by sealing the battery and storing it at room temperature 24 hours, the battery is charged at 0.1C (C is the charge and discharge rate of the battery, the same below) for 3 hours, and then stored at a temperature of 45°C for 24 hours, the battery is charged at 0.1C for 15 hours, and discharged at 0.5C to 1.0V. Change to 0.2C and discharge to 1.0V, then charge at 0.5C for 2.5 hours, discharge at 0.5C to 1.0V, and then change to 0.2C and discharge to 1.0V to complete the formation of the battery.

The performance difference between the battery of the present invention and the common AA-type nickel-hydrogen battery with a capacity of 2000mAh made of Ni(OH) ₂ is illustrated below with experimental data.

The experiment tests the battery capacity according to the requirements of IEC61951-2 and GB/T15100-2003. After the battery is fully discharged, use the AC impedance method to test the internal resistance of the battery in accordance with the requirements of IEC61951-2GB and T15100-2003.

The battery life is tested by 1C charge-discharge accelerated cycle, and the termination capacity is 80% of the initial capacity. The battery life test results are shown in Table 1:

Table 1

Test capacity recovery ratio after one year storage at room temperature: charge the battery at 0.1C for 16 hours, discharge at 0.2C to 1.0V, charge at 0.1C for 16 hours, store at room temperature 20±5℃ for one year, then charge the battery at 0.1C Charge, discharge to 1.0V at 0.2C, and store at room temperature for one year. The test results of capacity recovery ratio are shown in Table 2:

Table 2 Invention scheme control plan battery serial number 1A 2A 3A 1B 2B 3B final battery voltage 1.221 1.227 1.224 1.154 1.148 1.151 Capacity before storage (mAh) 2031.5 2054.3 2014.7 2028.4 2017.3 2047.5 Capacity after storage (mAh) 2023.4 2050.2 2002.6 1738.4 1736.9 1750.6 Capacity recovery rate 99.6% 99.8% 99.4% 85.7% 86.1% 85.5% average recovery rate 99.6% 85.8%

Short-circuit test capacity recovery ratio: charge the battery at 0.1C for 16 hours, discharge at 0.2C to 1.0V, and then charge at 0.1C for 16 hours, connect the battery to a 2Ω resistor, and short-circuit the battery at 45°C for 7 days, then charge the battery at 0.1C After charging for 16 hours and discharging to 1.0V at 0.2C, the test results of short-circuit capacity recovery ratio are shown in Table 3:

table 3 Invention scheme control plan battery serial number 1A 2A 3A 1B 2B 3B Initial capacity (mAh) 2042.6 2061.2 2038.4 2031.3 2018.2 2026.4 first week after short circuit Capacity (mAh) 2020.1 2011.7 2018.0 1661.6 1638.8 1639.4 Capacity recovery rate 98.9% 97.6% 99.0% 81.8% 81.2% 80.9% second week after short circuit Capacity (mAh) 2034.4 2036.5 2030.2 1647.4 1640.8 1653.5 Capacity recovery rate 99.6% 98.8% 99.6% 81.1% 81.3% 81.6% 3rd week after short circuit Capacity (mAh) 2058.9 2055.0 2052.7 1655.5 1644.8 1645.4 Capacity recovery rate 99.8% 99.7% 99.7% 81.5% 81.5% 81.2%

Test charge retention: charge the battery at 0.1C for 16 hours, discharge at 0.2C to 1.0V, charge at 0.1C for 16 hours, store at room temperature 20±5°C for 28 days, then discharge the battery at 0.2C to 1.0V , the battery remaining capacity test results are shown in Table 4:

Table 4 Invention scheme control plan battery serial number 1A 2A 3A 1B 2B 3B Initial capacity (mAh) 2049.1 2071.6 2064.3 2035.4 2026.5 2041.2 Residual capacity(mAh) 1749.9 1783.6 1771.2 1540.8 1517.8 1539.1 remaining capacity ratio 85.4% 86.1% 85.8% 15.7% 74.9% 75.4% average ratio 84.53% 75.33%

The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be assumed that the specific implementation of the present invention is limited to these descriptions. For those of ordinary skill in the technical field of the present invention, without departing from the concept of the present invention, they can also make some simple deduction or replacement, which should be regarded as belonging to the patent of the present invention determined by the submitted claims. protected range.

Claims (5)

1. One kind can be long time stored Ni-H cell, comprise positive plate, negative plate, be in the electrolyte of barrier film, housing and injection housing between the positive/negative plate, it is characterized in that:

   The active material of positive plate is the hydroxide nickel (OH) of cladding hydroxy cobalt oxide β-CoOOH ₂, the Ni of described coating beta-CoOOH (OH) ₂Adopt the following steps preparation successively:

   1) under 45 ℃～50 ℃ of temperature, ratio according to mole is Ni: Co: Zn=1: (0.02～0.05): (0.04～0.08), the cobalt sulfate solution of the zinc sulfate solution of the nickel sulfate solution of concentration 2.8mol/L～3.0mol/L, concentration 2.8mol/L～3.0mol/L and concentration 2.8mol/L～3.0mol/L is injected reactor respectively to be mixed, little by little drip the sodium hydrate aqueous solution of concentration 3mol/L～5mol/L then, with pH value stabilization to 13～14, under constantly stirring, make nickel, zinc, the whole crystallizations of cobalt ions;

   2) cobalt sulfate solution with concentration 2.8mol/L～3.0mol/L adds in the reactor gradually, the cobalt addition be nickel mole 4.6%～5.4%, with pH value stabilization to 9～10, make the cobalt ions crystallization coat Ni (OH) ₂The surface with deionized water wash hydroxide repeatedly, makes the pH value change into 7～8 again, dewaters then, dries and made β-Co (OH) ₂The zincification Ni (OH) of coating layer ₂

   3) be that the NaOH aqueous solution of 68wt～72wt% drops to the above-mentioned β of having-Co (OH) with concentration ₂The zincification Ni (OH) of coating layer ₂In, after complete haptoreaction took place for both under constantly stirring, the consumption that makes the NaOH aqueous solution was above-mentioned prepared β-Co (OH) ₂The zincification Ni (OH) of coating layer ₂Weight 8%～12%, in the heat baking 1.2 hours～1.8 hours down of 90 ℃～110 ℃ of temperature, make β-Co (OH) ₂Coating layer is oxidized to β-CoOOH coating layer, at last with deionized water wash and to adjust the pH value be 7～8, dewaters, dries the Ni (OH) that makes coating beta-CoOOH again ₂
2. 2. according to the described Ni-H cell that can be long time stored of claim 1, it is characterized in that:

   Described electrolyte is to comprise soluble bromide KBr, NaBr, NiBr ₂Or CoBr ₂Alkaline electrolyte.
3. One kind can be long time stored the manufacture method of Ni-H cell, it is characterized in that: following steps are arranged successively:

   (1) make positive and negative plate:

   The Ni (OH) for preparing coating beta-CoOOH earlier ₂, adopt the Ni (OH) of coating beta-CoOOH again ₂, be that skeleton adds binding agent making positive plate, the Ni of described preparation coating beta-CoOOH (OH) with the collector ₂Following steps are arranged successively:

   1) under 45 ℃～50 ℃ of temperature, ratio according to mole is Ni: Co: Zn=1: (0.02～0.05): (0.04～0.08), the cobalt sulfate solution of the zinc sulfate solution of the nickel sulfate solution of concentration 2.8mol/L～3.0mol/L, concentration 2.8mol/L～3.0mol/L and concentration 2.8mol/L～3.0mol/L is injected reactor respectively to be mixed, little by little drip the sodium hydrate aqueous solution of concentration 3mol/L～5mol/L then, with pH value stabilization to 13～14, under constantly stirring, make nickel, zinc, the whole crystallizations of cobalt ions;

   2) cobalt sulfate solution with concentration 2.8mol/L～3.0mol/L adds in the reactor gradually, the cobalt addition be nickel mole 4.6%～5.4%, with pH value stabilization to 9～10, make the cobalt ions crystallization coat Ni (OH) ₂The surface with deionized water wash hydroxide repeatedly, makes the pH value change into 7～8 again, dewaters then, dries and made β-Co (OH) ₂The zincification Ni (OH) of coating layer ₂

   3) be that the NaOH aqueous solution of 68wt～72wt% drops to the above-mentioned β of having-Co (OH) with concentration ₂The zincification Ni (OH) of coating layer ₂In, after complete haptoreaction took place for both under constantly stirring, the consumption that makes the NaOH aqueous solution was above-mentioned prepared β-Co (OH) ₂The zincification Ni (OH) of coating layer ₂Weight 8%～12%, in the heat baking 1.2 hours～1.8 hours down of 90 ℃～110 ℃ of temperature, make β-Co (OH) ₂Coating layer is oxidized to β-CoOOH coating layer, at last with deionized water wash and to adjust the pH value be 7～8, dewaters, dries the Ni (OH) that makes coating beta-CoOOH again ₂

   With the collector is that skeleton adds binding agent making negative plate;

   (2) assembled battery: the collocation of moulding positive and negative plate and barrier film is packed into behind the battery case, through annotating electrolyte, sealing;

   (3) battery changes into: the battery after will sealing, the time that ageing is set under the temperature of setting.
4. 4. according to the manufacture method of the described Ni-H cell that can be long time stored of claim 3, it is characterized in that:

   Described electrolyte is proportioning according to the ratio of mole is KOH: LiOH: NaOH: (KBr, NaBr, NiBr ₂Or CoBr ₂)=(5～8): (0.1～1.0): (0.1～3.0): the aqueous solution of (0.001～0.100).
5. 5. according to the manufacture method of the described Ni-H cell that can be long time stored of claim 4, it is characterized in that:

   Described binding agent is a kind of or any two or more mixture of the polytetrafluoroethylene PTFE aqueous solution, the CMC CMC aqueous solution, the hydroxypropyl methylcellulose HPMC aqueous solution, the PVAC polyvinylalcohol L aqueous solution, the Sodium Polyacrylate PAAS aqueous solution, the styrene butadiene rubber sbr aqueous solution.