CN100595316C - Method for preparing hydrogen-storing alloy powder - Google Patents
Method for preparing hydrogen-storing alloy powder Download PDFInfo
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- CN100595316C CN100595316C CN200610167396A CN200610167396A CN100595316C CN 100595316 C CN100595316 C CN 100595316C CN 200610167396 A CN200610167396 A CN 200610167396A CN 200610167396 A CN200610167396 A CN 200610167396A CN 100595316 C CN100595316 C CN 100595316C
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- 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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
A preparation method of a hydrogen storage alloy powder comprises the step of cladding a metal on the surface on the hydrogen storage alloy powder, wherein the method also includes at least one hydrogen absorption and desorption processes. The hydrogen absorption process includes contacting the hydrogen storage alloy with hydrogen gas above 0.1 MPa, and the hydrogen desorption process comprises vacuumizing the hydrogen storage alloy obtained in the hydrogen absorption process to a pressure below 1*10<4>. A battery prepared by the hydrogen storage alloy provided by the invention has good cycleperformance, high discharge capacity and long service life.
Description
Technical field
The invention relates to a kind of preparation method of hydrogen-storage alloy powder.
Summary of the invention
In recent years, because the development of mobile electronic device and the revolution of traffic power source, the research and development of the high tension battery energy have become the focus of countries in the world academia and Industrial Revolution.Nickel metal hydride battery is because of energy height, good, pollution-free, the memory-less effect of security, price suits and is subjected to extensive attention, be one of main supplying cell type of digital camera, for example common No. five (AA type) nickel-hydrogen secondary cells promptly are nickel-hydrogen secondary cells (Ni/MH) of using always.
The Ni/MH secondary rechargeable battery is in order to satisfy the demand of electronic product at present, and just the direction towards heavy body and high cycle performance develops.But, when therefore being immersed in the highly basic electrolytic solution, usually facing serious chemical corrosion and galvanic corrosion problem, thereby cause cycle performance to descend as the hydrogen-storage alloy of negative material because the electrolytic solution of nickel metal hydride battery is generally strong electrolytic solution.
The problem that cell container that causes in order to solve the negative pole alloy corrosion and cycle performance descend, the surface coats to handle and is introduced in very early in the middle of the hydrogen-storage alloy preparation process, promptly coat the corrosion resistant metallic membrane of one deck at alloy surface, alleviate the corrosion of alloy surface, prolong the cycle life of alloy electrode.For example, CN 1094807C discloses a kind of chemical nickel-plating method for surface of nickel-base alloy powder, this method comprises carries out acid treatment with alloy powder, carry out chemical nickel plating then in end liquid, liquid of the described end contains single nickel salt 60-100 grams per liter, trisodium citrate 20-40 grams per liter, ammonia chloride 10-35 grams per liter, sodium hypophosphite 20-50 grams per liter, sodium hydroxide 10-30 grams per liter.
Use the initial stage at battery, contain through the battery that coats the hydrogen-storage alloy of handling and compare with the battery of the hydrogen-storage alloy that contains uncoated processing, loading capacity and cycle performance obviously will be got well.But along with increasing of cycle index, discharge capacity of the cell descends very fast, and cycle performance is variation also.Therefore, battery is still very short work-ing life.
Summary of the invention
The objective of the invention is shortcoming low for the discharge capacity of the cell that overcomes the hydrogen-storage alloy that contains existing method preparation, the cycle performance difference, a kind of preparation method that can improve the hydrogen-storage alloy powder of nickel-hydrogen secondary cell loading capacity and cycle performance is provided.
Hydrogen-storage alloy can suppress the corrosion of electrolytic solution to hydrogen-storage alloy really after having coated metallic membrane, can improve cell container and cycle performance.But the present inventor finds that after deliberation hydrogen-storage alloy is put the hydrogen behavior owing to constantly inhale in charge and discharge process, and can cause that the hydrogen-storage alloy particulate expands and contraction, thereby causes breaking of alloying pellet, exposes the alloy internal surface.Therefore, along with increasing of cycle index, the electrolytic solution in the battery can enter between the disruptive alloying pellet, causes the hydrogen-storage alloy corrosion, thereby makes cell container reduce the cycle performance variation.
The invention provides a kind of preparation method of hydrogen-storage alloy powder, this method is included in the hydrogen-storage alloy powder surface clad, wherein, before clad metal, also comprise and at least once inhale the hydrogen process and put the hydrogen process, described suction hydrogen process comprises described hydrogen-storage alloy contacted with hydrogen more than pressure is 0.1 MPa, and the described hydrogen process of putting comprises that to be evacuated to pressure be 1 * 10 with inhaling hydrogen-storage alloy that the hydrogen process obtains
4Below the handkerchief.
The present invention is put the hydrogen processing by hydrogen-storage alloy powder is inhaled earlier before clad metal, hydrogen-storage alloy hydrogen causes efflorescence, make hydrogen-storage alloy powder put in the hydrogen process inhaling once more, particulate expands, the contraction behavior reduces, weakens, thereby avoid breaking of alloying pellet, metallic cover Stability Analysis of Structures ground is existed, thereby keep battery to have excellent cycle performance, prolong the work-ing life of battery.For example, 500 circulation back capacity sustainment rates that adopt the battery that method of the present invention makes are more than 75%, and the battery that prior art makes only is about 60%.
In addition, hydrogen-storage alloy coats after hydrogen causes efflorescence in advance again, makes the hydrogen-storage alloy resistance to corrosion strengthen, and therefore, the battery that the hydrogen-storage alloy that adopts the present invention to make is made has higher loading capacity.
Description of drawings
Fig. 1 is put the change curve of hydrogen cycle index for the average particle diameter of hydrogen-storage alloy powder with suction.
Embodiment
According to the present invention, after described hydrogen-storage alloy powder is inhaled earlier and is put hydrogen and handle hydrogen and cause efflorescence, clad metal again.Described suction is put the hydrogen process for earlier placing hydrogen atmosphere to inhale hydrogen hydrogen-storage alloy powder, vacuumizes the hydrogenolysis that makes in the alloy then and analyses and emit, thereby make the hydrogen-storage alloy efflorescence.
The suction hydrogen of described hydrogen-storage alloy can be implemented in the hydrogen atmosphere that pressure is pressed greater than the absorption hydrogen platform, and described suction hydrogen platform is pressed and is meant that inhaling hydrogen balance presses the pressure that no longer changes with hydrogen.Suction hydrogen process of the present invention comprises described hydrogen-storage alloy is contacted with hydrogen more than pressure is 0.1 MPa.Pressure raises suction hydrogen is speeded up, and hydrogen causes the efflorescence effect and improves, but there is saturation value in the hydrogen-storage alloy powder hydrogen, when hydrogen surpassed saturation value, pressure boost can not produce further effect to hydrogen-storage alloy yet again, and hypertonia, to the also corresponding raising of the requirement of equipment.Therefore, the preferred described hydrogen-storage alloy of the present invention and pressure are that the hydrogen of 0.1-5 MPa contacts.
The described hydrogen of putting is by the method that vacuumizes hydrogenolysis in the hydrogen-storage alloy to be analysed to emit.The hydrogen process of putting of the present invention comprises that it is 1 * 10 that the hydrogen-storage alloy that suction hydrogen process is obtained is evacuated to pressure
4Below the handkerchief.The pressure that vacuumizes is low more, and it is abundant more that hydrogen-storage alloy is put hydrogen, and it is also good more that hydrogen causes the efflorescence effect, and still, vacuum tightness is low more also high more to equipment requirements.Therefore, preferably being evacuated to pressure is 1 * 10
-5-1 * 10
2Handkerchief is put hydrogen.In addition, describedly put hydrogen more fast, fully in order to make, under the preferable case, described temperature of putting the hydrogen process is 40-300 ℃.
Suction of the present invention is put the hydrogen process need and is carried out more than 1 time, it is many more that the hydrogen multiplicity is put in suction, it is also good more that hydrogen causes the efflorescence effect, when but hydrogen caused efflorescence to certain number of times, hydrogen-storage alloy particulate particle dia value tended to stable gradually, at this moment, the increase suction is put the hydrogen number of times and can not made further change of hydrogen-storage alloy particle generation again, therefore in order to save the treatment time, enhance productivity, preferred described suction is put the hydrogen process and is carried out 1-70 time.
In addition, suction hydrogen process of the present invention and the number of times of putting the hydrogen process also can be represented with the particle dia that hydrogen-storage alloy powder hydrogen causes after the efflorescence.The number of times that the hydrogen process is put in described suction tends towards stability the average particle diameter of hydrogen-storage alloy powder and gets final product.Usually the stable average particle diameter of hydrogen-storage alloy powder is the 1-100 micron.
After hydrogen-storage alloy powder is put hydrogen, a spot of hydrogen is also contained in its inside, it can impact the hydrogen storage property of alloy powder, therefore, under the preferable case, put after the hydrogen process the last time and the plating clad metal before, comprise that also the hydrogen-storage alloy powder that will obtain heats, the temperature of described heating is 300-800 ℃, and the time of heating is 1-30 hour, and the pressure of heating is 1 * 10
-3-1 * 10
3Handkerchief.Further the temperature of preferred described heating is 300-700 ℃, and the time of heating is 1-24 hour, and the pressure during heating is 1 * 10
-3-1 * 10
2Handkerchief.
After hydrogen process and heat treated are put in suction; the hydrogen-storage alloy powder particles can ftracture; but some particle may ftracture and be insufficient; be the state that does not split that is in; this can influence the integrity of follow-up metallic cover; this inadequate particle that ftractures can't obtain to coat preferably, is therefore corroded easily in battery.Therefore, under the preferable case, the present invention also be included in put after the hydrogen process for the last time and the plating clad metal before, described hydrogen-storage alloy powder is vibrated, the size of vibration force makes after the hydrogen process is put in suction fully that rimose hydrogen-storage alloy particle fully ftractures.Described swing crushing can adopt conventional method, for example can adopt methods such as sonic oscillation, mechanical oscillation.The present invention preferably uses sonic oscillation, and the frequency of ultrasonic of described sonic oscillation can be 20-100kHz.After the vibration fragmentation, the hydrogen-storage alloy powder oven dry is got final product.The temperature of described oven dry can be 50-150 ℃, and the time can be 0.5-2 hour.
According to the present invention, the method for described metallic cover is conventionally known to one of skill in the art.For example, can coat in nickel, cobalt, the copper one or more.The method of described clad metal is that the mixture with described hydrogen-storage alloy powder and aqueous metal salt contacts with the aqueous solution of hypophosphite and gets final product.Described metal-salt is one or more in nickel salt, inferior cobalt salt, the mantoquita.For example, can be in the inferior cobalt of single nickel salt, nickelous nitrate, nickelous chloride, sulfuric acid, colbaltous nitrate, cobaltous chloride, copper sulfate, cupric nitrate, the cupric chloride one or more.The concentration of metal-salt is not less than 1.5 mol in the described aqueous metal salt, is preferably the saturated solution of 1.5 mol to this metal-salt.The weight ratio of described aqueous metal salt and hydrogen-storage alloy powder is 1-10: 1; The consumption of described sodium hypophosphite is the 2-25 weight % of hydrogen-storage alloy powder weight; The time of described contact is 5-20 minute.The pH value of preferred described aqueous metal salt is 7.5-9, and the temperature of described contact is 40-70 ℃.In addition, also can contain additive in the described metal water solution, for example, Trisodium Citrate, ammonium chloride etc., described sodium citrate concentration can be the 25-45 grams per liters, the concentration of described ammonium chloride can be the 20-45 grams per liter.
Under the preferable case, earlier described hydrogen-storage alloy powder is contacted with acid solution, the time of contact can be 2-4 minute.Described acid solution can be one or more in aqueous sulfuric acid, aqueous hydrochloric acid, the phosphate aqueous solution, the concentration of described acid solution can be the 0.1-1.5 mol, the consumption of described acid solution is to get final product by wetting hydrogen-storage alloy powder, is preferably 2-3 times of hydrogen-storage alloy powder.Described hydrogen-storage alloy powder with acid contact after, water washs.
Described hydrogen-storage alloy washes with water behind clad metal, and oven dry gets final product.
Among the present invention, described hydrogen-storage alloy powder can be the hydrogen-storage alloy powder with various chemical constitutions, for example can be AB
5, AB
2, AB, A
2In the Type B alloy powder one or more, wherein the A element is the heat-type metal that forms stable hydride easily, as titanium (Ti), zirconium (Zr), lanthanum (La), magnesium (Mg), calcium (Ca), mishmetal (Mm), the B element is the endothermic metal that is difficult to form hydride, as nickel (Ni), iron (Fe), cobalt (Co), manganese (Mn), copper (Cu), aluminium (Al).Described AB
5The type alloy powder comprises LaNi
5System, MmNi
5System, CaNi
5It is alloy powder.AB
2The type alloy powder comprises Ti
1.2Mn
1.8, TiCr
1.8, ZrMn
2, ZrV
2Alloy powder, A
2The Type B alloy powder comprises Mg
2Ni is an alloy powder.AB type alloy powder comprises TiFe, TiFe
0.8Mn
0.2MmNi
5An example that is alloy powder is MmNi
aCo
bAl
cMn
dThe type hydrogen-storage alloy powder, wherein, described a, b, c and d are all greater than 0, and 4.5＜a+b+c+d＜5.5.The preferred hydrogen-storage alloy powder of the present invention is MmNi
5Be alloy powder, especially be preferably MmNi
aCo
bAl
cMn
dThe type hydrogen-storage alloy powder, wherein, described a, b, c and d are all greater than 0, and 4.5＜a+b+c+d＜5.5.Above-mentioned hydrogen-storage alloy powder all is available commercially, and also can prepare.
The described hydrogen-storage alloy powder that is purchased or prepares can be directly used in the present invention, but if the hydrogen-storage alloy powder particles that is purchased or prepares is bigger, before hydrogen causes efflorescence, also can carry out coarse crushing earlier, make alloying pellet be decreased to below 1 centimetre, carry out hydrogen again and cause efflorescence, cause in the efflorescence and to inhale the number of times of putting hydrogen, raise the efficiency thereby can reduce hydrogen.Described coarse crushing can be undertaken by the method for mechanical disintegration.But, need to prove, it is different with the method that mechanical disintegration coats to identical particle diameter again that hydrogen of the present invention causes the method for carrying out clad metal after the efflorescence, simple mechanical disintegration just reduces the particle diameter of alloy powder, hydrogen-storage alloy powder is put in the hydrogen process inhaling, bigger expansion, contraction still will take place in particle, also can the ftractureing of alloying pellet, so the metallic cover structure is still unstable.
Below by embodiment method provided by the invention is described further.
Embodiment 1
Present embodiment illustrates the preparation method of hydrogen-storage alloy powder provided by the invention.
100 grams are consisted of MmNi
3.55Co
0.75Mn
0.4Al
0.3The hydrogen-storage alloy of (Guangdong Zhong Shan proud son of heaven rare earth material company limited produces, and average particle diameter is 200 microns) places sealed high-pressure vessel, and after feeding hydrogen to pressure-stabilisation was 0.5 MPa, vacuumizing and putting hydrogen to pressure was 1 handkerchief, stops then vacuumizing.Repeat above-mentioned suction and put the hydrogen process 50 times.After putting the hydrogen end of processing, measure average particle diameter with particle size distribution analysis instrument (Mastersizer2000, Britain Ma Erwen Instr Ltd.) at every turn.The result as shown in Figure 1.
Then, this alloy powder is placed the hydrochloric acid soln of 0.1 mol, soaked 3 minutes, filtering separation obtains solid matter, with 3 washings of 0.3 liter distillation moisture.Solid matter after this washing is joined in 1 liter of nickel sulfate solution, the concentration of described nickel sulfate solution is 1.5 mol, the pH value of described nickel sulfate solution is 7.5, temperature is 65 ℃, add the Trisodium Citrate of 40 grams, the ammonium chloride of 35 grams and the sodium hypophosphite of 15 grams then successively, carry out metallic cover, the reaction times is 5 minutes, filtering separation obtains solid matter then, with 3 washings of 0.3 liter distillation moisture.Heated 1 hour down at 50 ℃, promptly get hydrogen-storage alloy powder A1.
Comparative Examples 1
The preparation method of the hydrogen-storage alloy powder that this Comparative Examples explanation prior art provides.
100 grams are consisted of MmNi
3.55Co
0.75Mn
0.4Al
0.3The hydrogen-storage alloy of (Guangdong Zhong Shan proud son of heaven rare earth material company limited produces, and average particle diameter is 200 microns) places the hydrochloric acid soln of 0.1 mol, soaks 3 minutes, and filtering separation obtains solid matter, with 3 washings of 0.3 liter distillation moisture.Solid matter after this washing is joined in 1 liter of nickel sulfate solution, the concentration of described nickel sulfate solution is 1.5 mol, the pH value of described nickel sulfate solution is 7.5, temperature is 65 ℃, add the Trisodium Citrate of 40 grams, the ammonium chloride of 35 grams and the sodium hypophosphite of 15 grams then successively, carry out metallic cover, the reaction times is 5 minutes, filtering separation obtains solid matter then, with 3 washings of 0.3 liter distillation moisture.Heated 1 hour down at 50 ℃, promptly get hydrogen-storage alloy powder D1.
Comparative Examples 2
100 grams are consisted of MmNi
3.55Co
0.75Mn
0.4Al
0.3The hydrogen-storage alloy of (Guangdong Zhong Shan proud son of heaven rare earth material company limited produces, and average particle diameter is 200 microns) carries out mechanical mill, and being crushed to average particle diameter is 28 microns.
Then, this alloy powder is placed the hydrochloric acid soln of 0.1 mol, soaked 3 minutes, filtering separation obtains solid matter, with 3 washings of 0.3 liter distillation moisture.Solid matter after this washing is joined in 1 liter of nickel sulfate solution, the concentration of described nickel sulfate solution is 1.5 mol, the pH value of described nickel sulfate solution is 7.5, temperature is 65 ℃, add the Trisodium Citrate of 40 grams, the ammonium chloride of 35 grams and the sodium hypophosphite of 15 grams then successively, carry out metallic cover, the reaction times is 5 minutes, filtering separation obtains solid matter then, with 3 washings of 0.3 liter distillation moisture.Heated 1 hour down at 50 ℃, promptly get hydrogen-storage alloy powder D2.
Embodiment 2
Present embodiment illustrates the preparation method of hydrogen-storage alloy powder provided by the invention.
100 grams are consisted of MmNi
3.55Co
0.75Mn
0.4Al
0.3(Guangdong Zhong Shan proud son of heaven rare earth material company limited produces, average particle diameter is 200 microns) hydrogen-storage alloy place sealed high-pressure vessel, after feeding hydrogen to pressure-stabilisation is 2.5 MPas, high pressure vessel is heated to 100 ℃ then, vacuumizing and putting hydrogen to pressure is 1 * 10
-2Handkerchief stops to vacuumize then, and high pressure vessel is cooled to room temperature.Repeat above-mentioned suction and put the hydrogen process 50 times.
Then, this alloy powder is placed the hydrochloric acid soln of 0.1 mol, soaked 3 minutes, filtering separation obtains solid matter, with 3 washings of 0.3 liter distillation moisture.Solid matter after this washing is joined in 1 liter of nickel sulfate solution, the concentration of described nickel sulfate solution is 1.5 mol, the pH value of described nickel sulfate solution is 7.5, temperature is 65 ℃, add the Trisodium Citrate of 40 grams, the ammonium chloride of 35 grams and the sodium hypophosphite of 15 grams then successively, carry out metallic cover, the reaction times is 5 minutes, filtering separation obtains solid matter then, with 3 washings of 0.3 liter distillation moisture.Heated 1 hour down at 50 ℃, promptly get hydrogen-storage alloy powder A2.
Embodiment 3
Method according to embodiment 2 prepares hydrogen-storage alloy powder, and different is, inhale for the 50th time put hydrogen and finish after, this hydrogen-storage alloy powder is heated in this high pressure vessel again, temperature is 500 ℃, is incubated 12 hours, vacuumizes in the time of heating, pressure is 1 * 10
-3Handkerchief.And then clad metal.Make hydrogen-storage alloy powder A3 at last.
Embodiment 4
Method according to embodiment 3 prepares hydrogen-storage alloy powder, different is, is vacuumizing heat tracing under 500 ℃ after 12 hours, places 0.5 liter distilled water to vibrate 20 minutes under the ultrasonic wave of 50K hertz again, filtering separation obtains solid matter then, heats 2 hours down at 80 ℃.And then clad metal.Make hydrogen-storage alloy powder A4 at last.
Method according to embodiment 1 prepares hydrogen-storage alloy powder, and different makes, and it is 30 times that the hydrogen process is put in described suction.Make hydrogen-storage alloy powder A5 at last.
Embodiment 6
Method according to embodiment 1 prepares hydrogen-storage alloy powder, and different makes, and it is 10 times that the hydrogen process is put in described suction.Make hydrogen-storage alloy powder A6 at last.
Embodiment 7
Negative pole and the battery and their preparation method of the nickel-hydrogen secondary cell of hydrogen-storage alloy powder provided by the invention adopted in the explanation of this example.
(1) anodal preparation
With the nickel hydroxide of 100 weight parts, the CoO of 5 parts of weight (cobaltous oxide), the carboxymethyl cellulose binder of 0.2 part of weight reaches 30 parts of weight deionized waters and fully stirs, and is mixed into pasty slurry.Get regular foam nickel, be made into 91 millimeters * 42 millimeters * 1.4 millimeters nickel foam substrate after pressure, the cut-parts, nickel strap 20 millimeters * 1.5 millimeters * 0.2 millimeter of the mid-way of nickel foam substrate spot welding, nickel strap exposes 10 millimeters of nickel screens, fill the above-mentioned slurry that obtains, oven dry, roll-in make and are of a size of 91 millimeters * 42 millimeters * 1.4 millimeters positive pole then.Wherein, the content of positive electrode active materials is about 8 grams.
(2) preparation of negative pole
The hydrogen-storage alloy powder that 100 weight part embodiment 1 are obtained, carboxymethyl cellulose binder and 20 parts of weight deionized waters of 0.5 weight part fully stir, and are mixed into pasty slurry.This slurry is coated on the Punching steel strip equably, oven dry, roll-in then, cuts to make and be of a size of 172 millimeters * 42.5 millimeters * 0.5 millimeter negative pole, wherein, the amount of negative active core-shell material is about 9 grams.
(3) assembling of battery
The negative pole that positive pole, dividing plate (grafted polypropylene diaphragm), (2) that (1) is obtained obtain stacks gradually the electrode group that is wound into scroll, the electrode that obtains is assembled in the AA shaped steel shell, (electrolytic solution is KOH and LiOH mixed aqueous solution to add electrolytic solution 1.1g/Ah, the LiOH that contains 30 weight %KOH and 15 grams per liters in the mixed aqueous solution), make nickel-hydrogen secondary cell B1 after the sealing.
Comparative Examples 3-4
Method according to embodiment 7 prepares battery, and different is that described negative active core-shell material is respectively hydrogen-storage alloy powder D1 and the D2 that Comparative Examples 1-2 obtains.Make nickel-hydrogen secondary cell DD1 and DD2.
Embodiment 8-12
Method according to embodiment 7 prepares battery, and different is that described negative active core-shell material is respectively the hydrogen-storage alloy powder A2-A6 that embodiment 2-6 obtains.Make nickel-hydrogen secondary cell B2-B6.
Embodiment 13
The performance of the battery that present embodiment explanation the present invention makes.
(1) anodal weight ratio capacity
The battery B1 that embodiment 7 is made shelves half an hour with the electric current constant current charge of 0.3C (630 milliamperes) 5 hours, again with 0.3C electric current constant-current discharge to being 1.0V by voltage, the loading capacity first of record battery is calculated the anodal weight ratio capacity of battery then.The result is as shown in table 1.
Wherein, the quality of loading capacity/positive electrode active materials of anodal weight ratio capacity=first.
(2) cycle performance test
Under 20 ℃, the battery B1 that embodiment 7 is made ends to-Δ V=10mV with the current charges of 1C, current discharge to cell voltage with 1C is 1.0V again, carry out charge and discharge cycles, repeat above step 500 time, obtain the capacity of 500 circulation backs of battery 1C current discharge, then capacity sustainment rate before and after the computation cycles to 1.0V.The result is as shown in table 1.
Wherein, capacity sustainment rate=(the 500th circulation back loading capacity/cyclic discharge capacity) first * 100%
Comparative Examples 5-6
Method according to embodiment 13 is carried out performance test to battery DD1 and the DD2 that Comparative Examples 3-4 makes.The result is as shown in table 1.
Embodiment 14-18
Method according to embodiment 13 is carried out performance test to the battery B2-B6 that embodiment 7-12 makes.The result is as shown in table 1.
Table 1
| The battery source | The battery numbering | Anodal weight ratio capacity (MAH/gram) | Capacity sustainment rate (%) |
| Embodiment 7 | B1 | 295 | 83 |
| Comparative Examples 3 | DD1 | 250 | 55 |
| Comparative Examples 4 | DD2 | 240 | 60 |
| Embodiment 8 | B2 | 300 | 86 |
| Embodiment 9 | B3 | 310 | 89 |
| |
B4 | 320 | 92 |
| Embodiment 11 | B5 | 290 | 79 |
| Embodiment 12 | B6 | 285 | 75 |
As can be seen from Table 1,500 circulation back capacity sustainment rates of the battery B1-B6 that embodiment of the invention 7-12 makes are more than 75%, and battery DD1 that Comparative Examples 1 and Comparative Examples 2 make and DD2 only are about 60%.Therefore, the hydrogen-storage alloy powder that adopts the present invention to make can increase substantially the cycle performance of battery as the negative material of nickel-hydrogen secondary cell.
In addition, the anodal weight ratio capacity of the battery B1-B6 that makes of embodiment of the invention 7-12 all will be higher than Comparative Examples 3 battery DD1.Comparative Examples 4 makes battery DD2 because hydrogen-storage alloy particulate average particle diameter is less, though the capacity sustainment rate improves, its capacity significantly reduces, and along with the battery cycle index increases, its capacity descends very fast, and battery is short work-ing life.
Claims (10)
1, a kind of preparation method of hydrogen-storage alloy powder, this method is included in the hydrogen-storage alloy powder surface clad, it is characterized in that, before clad metal, also comprise and at least once inhale the hydrogen process and put the hydrogen process, described suction hydrogen process comprises described hydrogen-storage alloy contacted with hydrogen more than pressure is 0.1 MPa, and the described hydrogen process of putting comprises that to be evacuated to pressure be 1 * 10 with inhaling hydrogen-storage alloy that the hydrogen process obtains
4Below the handkerchief; Put after the hydrogen process the last time and the plating clad metal before, comprise that also the hydrogen-storage alloy powder that will obtain heats, the temperature of described heating is 300-800 ℃, the time of heating is 1-30 hour, the pressure of heating is 1 * 10
-3-1 * 10
3Handkerchief.
2, method according to claim 1, wherein, described suction hydrogen process is 1-70 time with the number of times of putting the hydrogen process.
3, method according to claim 1, wherein, the pressure of inhaling hydrogen process hydrogen is the 0.1-5 MPa, the pressure of putting the hydrogen process is 1 * 10
-5-1 * 10
2Handkerchief.
4, according to any described method among the claim 1-3, wherein, described temperature of putting the hydrogen process is 40-300 ℃.
5, method according to claim 1, wherein, the temperature of described heating is 300-700 ℃, and the time of heating is 1-24 hour, and the pressure of heating is 1 * 10
-3-1 * 10
2Handkerchief.
6, method according to claim 1, wherein, put after the hydrogen process the last time and the plating clad metal before, described hydrogen-storage alloy powder is vibrated, the size of vibration force makes after the hydrogen process is put in suction fully that rimose hydrogen-storage alloy particle fully ftractures.
7, method according to claim 6, wherein, described vibration is ultrasonic vibration, vibrational frequency is 20-100kHz.
8, method according to claim 1, wherein, the method for described clad metal is that the mixture with described hydrogen-storage alloy powder and aqueous metal salt contacts with the aqueous solution of hypophosphite; The concentration of metal-salt is not less than 1.5 mol in the described aqueous metal salt, and the weight ratio of described aqueous metal salt and hydrogen-storage alloy powder is 1-10: 1; Described hypophosphite is a sodium hypophosphite, and the consumption of described sodium hypophosphite is the 2-25 weight % of hydrogen-storage alloy powder weight; The time of described contact is 5-20 minute.
9, method according to claim 8, wherein, described metal-salt is one or more in nickel salt, inferior cobalt salt, the mantoquita.
10, according to the described method of claim 1, wherein, described hydrogen-storage alloy powder is MmNi
aCo
bAl
cMn
dType hydrogen-storage alloy powder, wherein said Mm are one or more the mixing among rare earth element, Mg, the Ca, a, and b, c and d are all greater than 0, and 2＜a+b+c+d＜5.5.
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| CN103633339B (en) * | 2013-11-30 | 2016-01-20 | 内蒙古科技大学 | A kind of nano Ce O 2high power capacity RE-Mg-Ni base hydrogen-storing alloy of catalysis and preparation method thereof |
| CN106009045B (en) * | 2016-07-01 | 2019-02-15 | 中国科学院宁波材料技术与工程研究所 | A kind of microcapsule red phosphorus, preparation method and application |
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2006
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| 贮氢合金粉体包覆铜工艺. 池克等.电池，第25卷第5期. 1995 |
| 贮氢合金粉体包覆铜工艺. 池克等.电池，第25卷第5期. 1995 * |
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