CN110241350A - Cupric cobalt boron hydrogen storage material and its preparation method and application - Google Patents
Cupric cobalt boron hydrogen storage material and its preparation method and application Download PDFInfo
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- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
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Abstract
The present invention provides a kind of cupric cobalt boron hydrogen storage material and its preparation method and application, belongs to hydrogen storage material technical field.The expression formula of the material is Co2B+3wt%Cu, the copper are entered in cobalt boron material in the form of doping, are distributed in grain surface, or be coated on Co2On B alloy surface.The present invention also provides a kind of preparation methods of cupric cobalt boron hydrogen storage material, copper is added by the method that mechanical alloying and solution replacement coat respectively, preparation process is simple, highly-safe, strong operability, which effectively raises the cycle life and discharge capacity of battery.
Description
Technical field
The invention belongs to hydrogen storage material technical fields, and in particular to cupric cobalt boron hydrogen storage material and preparation method thereof and answer
With.
Background technique
Negative electrode material of the hydrogen bearing alloy as nickel-metal hydride battery, hydrogen storage property play to pass the performance of entire nickel-metal hydride battery
Important role.Therefore significant by improving the performance of the hydrogen storage property raising nickel-metal hydride battery of hydrogen bearing alloy.
The discharge capacity that can be seen that Co base hydrogenous alloy from current research achievement had exceeded be commercialized at present it is dilute
Soil series hydrogen bearing alloy AB5The theoretical discharge capacity (372mAh/g, LaNi5H6) of type alloy, and its cyclical stability is significantly larger than
Mg2Ni base (AB type hydrogen storage alloy) hydrogen bearing alloy.For example, Song great Wei etc. has been prepared for packet by electronation and Principles of Heating Processing
Structure C o-B alloy is covered, by annealing, initial Co-B alloy is decomposed into Co, B simple substance with clad structure of crystalline state.
The alloy initial discharge capacity reaches 550mAh/g, and after 80 charge and discharge, the charge-discharge performance of material reaches 400mAh/g.
Chung etc. is prepared for nanocrystalline ultra-fine Co powder with chemical reduction method and arc melting method respectively, which exists
410mAh/g or more, after 50 charge and discharge cycles, discharge capacity is stablized in 350mAh/g or so, shows good follow
Ring stability.Wang etc. has synthesized ultrafine amorphous Co-B alloy particle with chemical reduction method.In the charge-discharge velocity of 100mAh/g
Under, which is more than that 300mAh/g and traditional hydrogen storage material capacity are very nearly the same.In filling for 300mAh/g
Under discharge rate, after 100 charge and discharge cycles, which only decays 10%.Therefore, most of cobalt
Boron class alloy has large capacity hydrogen storage property.
The super Entropy Changes elements such as magnesium, lithium, potassium, sodium and zinc are added into hydrogen storage material, be promoted hydrogen storage material discharge capacity, times
The effective way of chemical property including rate discharge capability, representativeness invention are as follows: on May 2nd, 2012, Patent Office of the People's Republic of China disclosed
Entitled " AB4.7The CN102437317A patent of the super Entropy Changes method of non-stoichiometric hydrogen storage material ".The invention advantage is
By system of elementsization such as the magnesium added in prior art, lithium, potassium, sodium and zinc and preliminary theoryization arrives the height of " super Entropy Changes ".
On December 15th, 2010 Patent Office of the People's Republic of China disclose it is entitled " in hydrogen storage material be added magnesium, lithium, sodium and potassium fused salt
The CN101914699A patent of invention of electro synthesis method ".The advantages of invention, is magnesium, lithium, sodium and four kinds of potassium super Entropy Changes members
Element, by same fused-salt bath, with electric osmose and electrolysis, interaction mode is safe and effective is added in hydrogen storage material；However it is lacked
Point with: such Adding Way is all relatively high for the equipment requirement of degree of being skilled in technique requirement and fused salt electro synthesis indispensability,
Show slightly insufficient in terms of the small equal practicabilities of simple process and equipment investment.
The usual chemical activity of its simple substance of these elements such as magnesium, lithium, potassium, sodium is all very strong, except fused salt electro synthesis method is added to
Hydrogen storage material China and foreign countries, another effective method is mechanical alloying.It is listed in table 1 by these super Entropy Changes such as magnesium, lithium, potassium, sodium
The simple substance or compound of element are added in high-energy ball milling tank, synthesize hydrogen storage material by mechanical alloying method, Chinese special
Representative patents disclosed in sharp office are shown in Table 1.
Table 1
It is listed in table 1 that the simple substance or compound of these elements such as magnesium, lithium, potassium, sodium are added to benefit in high-energy ball milling tank
With the invention of mechanical alloying method synthesis hydrogen storage material, Common advantages are easy to operate, practical.
To sum up: by copper to be coated on Co2The cladding process and machine-alloying of B alloy microparticle surfaces, obtaining has super entropy
The hydrogen storage material and its manufacturing method for being denaturalized energy have no patent disclosure and article report.
Summary of the invention
The purpose of the invention is to provide cupric cobalt boron hydrogen storage material and its preparation method and application, cupric cobalt boron storage
Hydrogen material effectively raises the cycle life and discharge capacity of battery.
Present invention firstly provides a kind of cupric cobalt boron hydrogen storage material, expression formula Co2B+3wt%Cu, the copper are
Entered in cobalt boron material in the form of doping, is distributed in grain surface, or be coated on Co2On B alloy surface.
The present invention also provides a kind of preparation methods of cupric cobalt boron hydrogen storage material, include the following steps:
Step 1: according to Co2B hydrogen storage material ingredient expression formula weighs Co metal powder, B powder, is put into tube furnace after mixing
In anneal, obtain Co2B；
Step 2: the Co that step 1 is obtained2B machinery pulverizes, and obtains Co2B hydrogen storage material powder；
The Co that step 3: weighing Cu powder respectively and step 2 obtains2B hydrogen storage material powder, is put into ball milling in ball grinder, obtains
To cupric cobalt boron hydrogen storage material；The Cu powder and Co2The weight percent of B hydrogen storage material powder is 3wt%:97wt%；Or
Person has configured CuSO4Solution, the Co that step 2 is obtained2B hydrogen storage material powder pours into wherein, after stirring, filters out precipitating, obtains
To cupric cobalt boron hydrogen storage material, the CuSO4The quality of Cu is relative to Co in solution2The 3wt% of the quality of B.
Preferably, the step 1 specifically: the powder mixed is put into quartz boat, is then placed in tube furnace
In, after being sealed, by tube furnace vacuum state 2 × 10-1MPa-1×10-1MPa, preferably 1 × 10-1MPa is then charged with
High-purity argon gas to 1.1 ± 0.1 atmospheric pressure, extraction three times, is then turned on power supply, using Resistant heating, with adding for 5 DEG C/min
Thermal velocity heating keeps the temperature 10h, anneals, to obtain Co up to 800 DEG C2B hydrogen bearing alloy.
Preferably, the Co of the step 22B hydrogen storage material size of powder particles is 200~400 mesh.
Preferably, the ball grinder of the step 3 is stainless steel jar mill.
Preferably, the diameter of the stainless steel jar mill of the step 3 is 4~15mm.
Preferably, the vibration frequency of the ball grinder of the step 3 is 200~1000 revs/min.
Preferably, the ball material weight ratio of the step 3 is 10:1, and Ball-milling Time is 10~15min.
Preferably, the above-mentioned mixing time of the step 3 is 1~2min.
Application the present invention also provides above-mentioned cupric cobalt boron alloy material storing hydrogen as negative electrode material in the battery.
Beneficial effects of the present invention
(1) present invention provides a kind of cupric cobalt boron alloy material storing hydrogen, which is using cobalt boron hydrogen bearing alloy as base, respectively
Copper is added by the method that mechanical alloying and solution replacement coat, and preparation process is simple, highly-safe, strong operability, ball
Honed journey can be controlled by adjusting the quality of the Ball-milling Time of ball mill, ratio of grinding media to material and ball, guarantee Co2B structure
Successfully Cu is added to form cupric cobalt boron alloy material storing hydrogen under the premise of not being destroyed.
(2) copper in cupric cobalt boron hydrogen storage material of the invention enters in cobalt boron material in the form adulterated, distribution
In grain surface, so that cobalt boron material be made to reduce in the extent of corrosion of alkaline electrolyte solution, while reversible reaction is also increased
Dotted point, to improve battery cathode catalytic activity and cycle life.
(3) copper in cupric cobalt boron hydrogen storage material of the invention can also be the Cu in solution2+Replace Co2In B
Co, to be coated on Co2On B alloy surface, the Cu in this processing method is distributed more uniform, good dispersion, while also rising
Etch-proof effect is arrived.The results showed that after 50 circulations, the capacity attenuation rate of both cupric cobalt boron hydrogen bearing alloys
Lower than cobalt boron hydrogen bearing alloy；
Detailed description of the invention
Fig. 1 is Co2B, the XRD diagram for the cupric cobalt boron alloy material storing hydrogen that Examples 1 and 2 are prepared；
Fig. 2 is the ESD figure for the cupric cobalt boron alloy material storing hydrogen that embodiment 1 is prepared；
Fig. 3 is the ESD figure for the cupric cobalt boron alloy material storing hydrogen that embodiment 2 is prepared；
Fig. 4 is Co2B, the cupric cobalt boron alloy material storing hydrogen that Examples 1 and 2 are prepared is the mould of negative electrode active material
Quasi- circulating battery number and discharge capacity graph of relation.
Specific embodiment
Present invention firstly provides a kind of cupric cobalt boron hydrogen storage material, expression formula Co2B+3wt%Cu, the copper are
Entered in cobalt boron material in the form of doping, is distributed in grain surface, or be coated on Co2On B alloy surface.
Copper in cupric cobalt boron hydrogen storage material of the invention can be entered in cobalt boron material in the form of doping, distribution
In grain surface, so that cobalt boron material be made to reduce in the extent of corrosion of alkaline electrolyte solution, while reversible reaction is also increased
Dotted point, to improve battery cathode catalytic activity and cycle life；In addition, the copper can also be in solution
Cu2+Replace Co2Co in B, to be coated on Co2On B alloy surface, the Cu distribution in this processing method is more uniform, point
It is good to dissipate property, while also playing etch-proof effect.
The present invention also provides a kind of preparation methods of cupric cobalt boron hydrogen storage material, include the following steps:
Step 1: according to Co2B hydrogen storage material ingredient expression formula weighs Co metal powder, B powder, is put into tube furnace after mixing
In anneal, obtain Co2B；
Step 2: the Co that step 1 is obtained2B machinery pulverizes, and obtains Co2B hydrogen storage material powder；
The Co that step 3: weighing Cu powder respectively and step 2 obtains2B hydrogen storage material powder, is put into ball milling in ball grinder, obtains
To cupric cobalt boron hydrogen storage material；The Cu powder and Co2The weight percent of B hydrogen storage material powder is 3wt%:97wt%；Or
Person
CuSO is configured4Solution, the Co that step 2 is obtained2B hydrogen storage material powder pours into wherein, and after stirring, it is heavy to filter out
It forms sediment, obtains cupric cobalt boron hydrogen storage material, the CuSO4The quality of Cu is relative to Co in solution2The 3wt% of the quality of B.
The present invention is first, in accordance with Co2B hydrogen storage material ingredient expression formula weighs Co metal (purity 99.9%), B powder (purity
99.9%) it, after mixing, is then placed in tube furnace, anneals.
By above-mentioned small pieces by tube annealing, Co is prepared2B hydrogen bearing alloy, specifically comprises the processes of: the powder that will be mixed
End is put into quartz boat, is then placed in tube furnace, after being sealed, by tube furnace vacuum state 2 × 10-1MPa-1×10-1MPa, preferably 1 × 10-1MPa is then charged with high-purity argon gas to 1.1 ± 0.1 atmospheric pressure, and extraction three times, is then turned on electricity
Source keeps the temperature 10h, anneals, to obtain using Resistant heating with the heating speed heating of 5 DEG C/min up to 800 DEG C
Co2B hydrogen bearing alloy.
According to the present invention, by Co obtained above2B hydrogen bearing alloy mechanical lapping, the milling time are preferably
10min forms Co2B alloy material storing hydrogen powder, then with sifter device by Co2B hydrogen-bearing alloy powder is allocated as different size, preferably
Co2B hydrogen-bearing alloy powder size is between 200~400 mesh.
It by copper is entered in cobalt boron material in the form of doping according to the present invention, specifically: it will be obtained above
Co2B hydrogen-bearing alloy powder and pure copper powder are transferred in high-purity argon atmosphere and carry out ball milling in ball grinder, the ball material weight ratio
Preferably 10:1, Ball-milling Time are preferably 10-15min, and the ball grinder is preferably stainless steel jar mill, stainless steel jar mill
Diameter be preferably 4~15mm, the vibration frequency of ball grinder is preferably 200~1000 revs/min, and ball grinder is taken from ball mill
Under, ball grinder is opened in high-purity argon atmosphere glove box and obtains cupric cobalt boron hydrogen storage material, and is sealed to be placed in drier and be saved.
The copper powder and Co2The weight percent of B hydrogen-bearing alloy powder is 3wt%:97wt%.
Alternatively, copper is coated on Co2On B alloy surface, specifically:
First have to the CuSO of configuration 200ml4Solution is placed in the beaker that content volume is 300-500ml, preferably 400ml.
Then by Co obtained above2B hydrogen-bearing alloy powder is poured slowly into wherein, 1-2min is stirred with glass bar, by precipitating therein
It filters out, is washed three times with distilled water and absolute alcohol, be finally placed in a vacuum drying oven, setting drying temperature is 60~80
DEG C, it is taken out after dry 10~12h spare.The CuSO4Copper and Co in solution2The weight percent of B hydrogen-bearing alloy powder is
3wt%:97wt%.
The phase structure for the cupric cobalt boron hydrogen storage material that two methods of the invention obtain uses X-ray diffraction method (XRD) table
Sign, uses Cu-K α target when test, and continuous scanning speed is 5 °/min, and 10 °~80 ° of scanning range.
The cupric cobalt boron hydrogen storage alloy electrochemical hydrogen storage property test that two methods of the present invention obtain uses DC-5 type battery
Tester, test process carry out in simulation ni-mh experimental cell, battery production method specifically: by cupric cobalt boron of the invention
Hydrogen bearing alloy is as the active material in ni-mh experimental cell cathode, using the active material and 5 times of weight as the carbonyl of collector
Base nickel powder is uniformly mixed, and cools down the molded disk for diameter 10mm as the cathode of battery, the pole of the cathode using tablet press machine
Ear uses the nickel wire of diameter 1mm and is connect by impulsed spot welding mode with negative electrode tab, and the anode of experimental cell is sintered using commodity
Nickel hydroxide (Ni (OH)2/ NiOOH), the diaphragm between positive and negative anodes then selects the PP type of wetability and good air permeability
Diaphragm, electrolyte are the KOH aqueous solution of concentration 6M.
For a further understanding of the present invention, illustrate the present invention in further detail below with reference to embodiment, but the present invention is simultaneously
Not only it is defined in these embodiments.
CuSO used in embodiment4It is commercially available, purity 99.9% with copper powder, the granularity of copper powder is 200 mesh.
Embodiment 1
Cupric cobalt boron hydrogen storage material expression formula: Co2B+3wt%Cu (doping), the material preparation method are as follows:
(1) accurate weighing 9.16Co metal (purity 99.9%) and 0.84B nonmetallic (purity 99.9%), will weigh up
Powder uniformly mix, quartz ampoule will be sealed in there is the quartz boat of mixed uniformly powder to be put into the quartz ampoule of tube furnace,
It is 1 × 10 by tube furnace vacuum state-1MPa is then charged with protective gas high-purity argon gas to 1.1 ± 0.1 atmospheric pressure, takes out
It puts three times, is then turned on power supply, keep the temperature 10h with the heating speed heating of 5 DEG C/min up to 800 DEG C using Resistant heating,
It anneals, to obtain Co2B hydrogen bearing alloy.
(2) Co after the annealing for obtaining above-mentioned steps (1)2B alloy is put into agate and grinds in alms bowl, carries out machinery and pulverizes, when
Between be 10min, after the time arrives, by the alloy powder in crusher pour into sifter device carry out different size particle separation, Co2B
Hydrogen-bearing alloy powder size is between 200~400 mesh.
(3) the 10mg Co that accurate weighing above-mentioned steps (2) obtain respectively2B hydrogen-bearing alloy powder and 0.3mg copper powder, are filling
It is fitted into stainless steel jar mill in the glove box for having high-purity argon atmosphere and carries out ball milling, steel ball size 4mm, ratio of grinding media to material 10:1,
200 revs/min of vibration frequency, ball grinder is removed from ball mill, is beaten in high-purity argon atmosphere glove box by Ball-milling Time 10min
Grinding jar of kicking off obtains cupric cobalt boron hydrogen storage material, and seals to be placed in drier and save.
The XRD diagram for the cupric cobalt boron hydrogen storage material that embodiment 1 obtains is as shown in Figure 1, use Cu-K α target, continuously when testing
Scanning speed be 5 °/min, 10 °~80 ° of scanning range.
Fig. 2 is the ESD figure for the cupric cobalt boron alloy material storing hydrogen that embodiment 1 is prepared；Fig. 2 illustrates Co2B hydrogen bearing alloy
Surface distribution uniform.
Embodiment 2
Cupric cobalt boron hydrogen storage material expression formula: Co2B+3wt%Cu (cladding), the material preparation method are as follows
(1) accurate weighing 9.16Co metal (purity 99.9%) and 0.84B nonmetallic (purity 99.9%), will weigh up
Powder uniformly mix, quartz ampoule will be sealed in there is the quartz boat of mixed uniformly powder to be put into the quartz ampoule of tube furnace,
It is 1 × 10 by tube furnace vacuum state-1MPa is then charged with protective gas high-purity argon gas to 1.1 ± 0.1 atmospheric pressure, takes out
It puts three times, is then turned on power supply, keep the temperature 10h with the heating speed heating of 5 DEG C/min up to 800 DEG C using Resistant heating,
It anneals, to obtain Co2B hydrogen bearing alloy.
(2) Co after the annealing for obtaining above-mentioned steps (1)2B hydrogen bearing alloy is put into agate and grinds in alms bowl, carries out mechanical stone roller
Broken, the alloy powder in crusher after the time arrives, is poured into sifter device the separation for carrying out different size particle by time 10min,
Co2B hydrogen-bearing alloy powder size is between 200~400 mesh.
(3) the 10mg Co that accurate weighing above-mentioned steps (2) obtain respectively2B hydrogen-bearing alloy powder and 0.75mg CuSO4It is (pure
99.9%), to be poured into distilled water, stirring is completely dissolved degree to powder, is configured to the CuSO of 200ml4Solution.Then will
Co2B hydrogen-bearing alloy powder is poured slowly into wherein, stirs 1min with glass bar, original blue solution becomes purple solution, by it
In precipitating filter out, with distilled water and absolute alcohol by the ionic impurity washes clean on sediment surface, be finally placed in true
In empty drying box, setting drying temperature is 60 DEG C, and sealing, which is placed in drier, after dry 10h saves.
The XRD diagram for the cupric cobalt boron hydrogen storage material that embodiment 2 obtains is as shown in Figure 1, use Cu-K α target, continuously when testing
Scanning speed be 5 °/min, 10 °~80 ° of scanning range.
Fig. 3 is the ESD figure for the cupric cobalt boron alloy material storing hydrogen that embodiment 2 is prepared；Fig. 3 illustrates Co2B hydrogen bearing alloy
The distribution of surface C u is very uniform, and the abundance of the Cu in the material that obtains than example 2 of the abundance of unit area Cu is more.
Embodiment 3
The cupric cobalt boron hydrogen storage material and carbonyl nickel powder that Examples 1 to 2 is not obtained are uniformly mixed with weight ratio 1: 5,
The pressure for applying 8MPa to resulting mixture of powders waits the calm disk for being pressed into diameter 10mm and thickness 1.5mm as cathode,
The tab of the cathode uses the nickel wire of diameter 1mm and is connect by impulsed spot welding mode with negative electrode tab, and ni-mh experimental cell is just
Pole uses the nickel hydroxide (Ni (OH) of commodity sintering2/ NiOOH), the diaphragm between positive and negative anodes then selects wetability and gas permeability
Good PP type diaphragm, electrolyte are the KOH aqueous solution of concentration 6M.
It will be with Co2The cupric cobalt boron hydrogen bearing alloy that B alloy and Examples 1 to 2 obtain is the simulation electricity of negative electrode active material
Pond is tested for the property, specifically:
Enhancing rate calculation formula are as follows: capacity boost rate=[(" cupric cobalt boron hydrogen bearing alloy " discharge capacity-" control blank
Battery " discharge capacity)/the discharge capacity of " control use blank battery "] × 100%.
Attenuation rate calculation formula are as follows: capacity attenuation rate=[(follow for same battery maximum discharge capacity-same battery the 50th time
The discharge capacity of ring)/same battery maximum discharge capacity] × 100%.
Fig. 4 is with Co2The cupric cobalt boron hydrogen bearing alloy that B alloy and Examples 1 to 2 obtain is the simulation of negative electrode active material
Circulating battery number and discharge capacity graph of relation.In figure, curve 1 represents Co2B, curve 2 represent Co2B+3wt%Cu (mixes
It is miscellaneous), curve 3 represents Co2B+3wt%Cu (cladding), it can be seen from the figure that three kinds of battery first time charge discharges can
Reach maximum discharge capacity, cupric cobalt boron hydrogen storage material volume change is specifically as shown in table 2:
Table 2
Table 2 is with Co2The cupric cobalt boron hydrogen bearing alloy that B alloy and Examples 1 to 2 obtain is the simulation of negative electrode active material
The stable circulation performance data of battery, from table 2 it can be seen that with Co is included2The cathode of B alloy is compared, and of the invention two kinds contain
Copper cobalt boron hydrogen bearing alloy is that the simulated battery of negative electrode active material has excellent efficient discharge performance, and is prepared using cladding process
Cupric cobalt boron hydrogen bearing alloy it is more much better than the discharge performance of alloy prepared by another method.
Claims (10)
1. a kind of cupric cobalt boron hydrogen storage material, which is characterized in that its expression formula is Co2B+3wt%Cu, the copper are to adulterate
Form enter in cobalt boron material, be distributed in grain surface, or be coated on Co2On B alloy surface.
2. a kind of preparation method of cupric cobalt boron hydrogen storage material according to claim 1, which is characterized in that including walking as follows
It is rapid:
Step 1: according to Co2B hydrogen storage material ingredient expression formula weighs Co metal powder, B powder, is put into tube furnace and carries out after mixing
Annealing, obtains Co2B；
Step 2: the Co that step 1 is obtained2B machinery pulverizes, and obtains Co2B hydrogen storage material powder；
The Co that step 3: weighing Cu powder respectively and step 2 obtains2B hydrogen storage material powder, is put into ball milling in ball grinder, is contained
Copper cobalt boron hydrogen storage material；The Cu powder and Co2The weight percent of B hydrogen storage material powder is 3wt%:97wt%；
Or CuSO is configured4Solution, the Co that step 2 is obtained2B hydrogen storage material powder pours into wherein, and after stirring, it is heavy to filter out
It forms sediment, obtains cupric cobalt boron hydrogen storage material, the CuSO4The quality of Cu is relative to Co in solution2The 3wt% of the quality of B.
3. a kind of preparation method of cupric cobalt boron hydrogen storage material according to claim 2, which is characterized in that the step 1
Specifically: the powder mixed is put into quartz boat, is then placed in tube furnace, after being sealed, tube furnace is evacuated
State 2 × 10-1MPa-1×10-1MPa, preferably 1 × 10-1MPa, is then charged with high-purity argon gas to 1.1 ± 0.1 atmospheric pressure,
Extraction three times, is then turned on power supply, utilizes Resistant heating, with the heating speed heating of 5 DEG C/min up to 800 DEG C, heat preservation
10h anneals, to obtain Co2B hydrogen bearing alloy.
4. a kind of preparation method of cupric cobalt boron hydrogen storage material according to claim 2, which is characterized in that the step 2
Co2B hydrogen storage material size of powder particles is 200~400 mesh.
5. a kind of preparation method of cupric cobalt boron hydrogen storage material according to claim 2, which is characterized in that the step 3
Ball grinder be stainless steel jar mill.
6. a kind of preparation method of cupric cobalt boron hydrogen storage material according to claim 2, which is characterized in that the step 3
Stainless steel jar mill diameter be 4~15mm.
7. a kind of preparation method of cupric cobalt boron hydrogen storage material according to claim 2, which is characterized in that the step 3
Ball grinder vibration frequency be 200~1000 revs/min.
8. a kind of preparation method of cupric cobalt boron hydrogen storage material according to claim 2, which is characterized in that the step 3
Ball material weight ratio be 10:1, Ball-milling Time be 10~15min.
9. a kind of preparation method of cupric cobalt boron hydrogen storage material according to claim 2, which is characterized in that the step 3
Above-mentioned mixing time be 1~2min.
10. application of the cupric cobalt boron alloy material storing hydrogen described in claim 1 as negative electrode material in the battery.
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