CN104226985A - A kind of nickel plating modification method of AB3 type hydrogen storage alloy - Google Patents
A kind of nickel plating modification method of AB3 type hydrogen storage alloy Download PDFInfo
- Publication number
- CN104226985A CN104226985A CN201410299108.5A CN201410299108A CN104226985A CN 104226985 A CN104226985 A CN 104226985A CN 201410299108 A CN201410299108 A CN 201410299108A CN 104226985 A CN104226985 A CN 104226985A
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- CN
- China
- Prior art keywords
- alloy
- minutes
- type
- hydrogen storage
- nickel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000956 alloy Substances 0.000 title claims abstract description 43
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 43
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000007747 plating Methods 0.000 title claims abstract description 27
- 239000001257 hydrogen Substances 0.000 title claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 17
- 238000002715 modification method Methods 0.000 title abstract 2
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 230000006698 induction Effects 0.000 claims abstract description 6
- 238000002844 melting Methods 0.000 claims abstract description 6
- 230000008018 melting Effects 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract 2
- 150000002910 rare earth metals Chemical class 0.000 claims abstract 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims 1
- 238000005406 washing Methods 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract 1
- 238000005275 alloying Methods 0.000 description 8
- 239000008188 pellet Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 229910018095 Ni-MH Inorganic materials 0.000 description 6
- 229910018477 Ni—MH Inorganic materials 0.000 description 6
- 239000002243 precursor Substances 0.000 description 5
- 238000000498 ball milling Methods 0.000 description 4
- 239000001996 bearing alloy Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 230000004087 circulation Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明公开了一种AB3型储氢合金的镀镍改性方法。通过真空感应熔炼法制备AB3型Mm0.78Mg0.22Ni2.48Mn0.09Al0.23Co0.47（Mm为混合稀土，组成的重量百分比为：82.3%La和17.7%Nd）母体合金，合金锭机械粉碎后，球磨60～90分钟，筛分200～300目颗粒粉末；取2克颗粒粉末放入200mL镀液中，搅拌5分钟，加入50mLNaBH4溶液，搅拌20分钟，过滤，用去离子水和无水乙醇洗涤，在60℃下真空干燥6～10小时，制得表面镀镍的AB3型改性合金。本发明对AB3型储氢合金进行表面改性，制得具有较高放电容量、良好循环稳定性及优异动力学性能的合金电极。The invention discloses a nickel plating modification method of an AB 3 type hydrogen storage alloy. AB 3- type Mm 0.78 Mg 0.22 Ni 2.48 Mn 0.09 Al 0.23 Co 0.47 (Mm is mixed rare earth, composition weight percent: 82.3% La and 17.7% Nd) parent alloy was prepared by vacuum induction melting method, and the alloy ingot was mechanically pulverized, Ball mill for 60-90 minutes, sieve 200-300 mesh particle powder; take 2 grams of particle powder and put it into 200mL plating solution, stir for 5 minutes, add 50mL NaBH 4 solution, stir for 20 minutes, filter, wash with deionized water and absolute ethanol Washing and drying in vacuum at 60°C for 6-10 hours to obtain a nickel-plated AB 3 type modified alloy. The invention modifies the surface of the AB 3 type hydrogen storage alloy to prepare an alloy electrode with higher discharge capacity, good cycle stability and excellent kinetic performance.
Description
Technical field
The invention belongs to materials chemistry, metallurgical chemistry and electrochemical research field, particularly a kind of AB
3type Mm
0.78mg
0.22ni
2.48mn
0.09al
0.23co
0.47the nickel plating method of modifying of hydrogen bearing alloy.
Background technology
Worsen day by day serious today in energy crisis and environment, Hydrogen Energy enjoys the concern of people as a kind of clean energy resource.In the application of hydrogen energy source, hydrogen storage technology is the key factor of restriction hydrogen energy source development.In various hydrogen storage material, hydrogen bearing alloy is used as the negative material of Ni-MH battery with the advantage of its uniqueness.Ni-MH battery is owing to having the good characteristic of high-energy-density, high charging and discharging capabilities and environment compatibility, and be used on electronic product and hybrid electric vehicle, this is also the today developed rapidly at lithium ion battery, and Ni-MH battery still can exist and the reason place developed.At present, the negative material that the Ni-MH battery be commercially used uses is AB
5type hydrogen storage alloy, and its capacity is close to theoretical value, improves AB further
5it is more difficult that the capacity of type hydrogen storage alloy will become.The extensive use of generally application and the electric motor car of electronic product makes us more urgent to the needs of high energy battery, finds novel hydrogen storage material and replaces AB
5type hydrogen storage alloy, thus the capacity improving Ni-MH battery just seems very necessary.In recent years, researcher found AB
3type hydrogen storage alloy has high discharge capacity, but due to its easily oxidized and efflorescence in charge and discharge process, causes it to be restricted in actual applications.In order to make AB
3type hydrogen storage alloy can be applied better in Ni-MH battery, and researchers improve AB by preparing the methods such as composite alloy, heat treatment, element replacement, surface treatment
3the chemical property of type hydrogen storage alloy.Wherein, chemical nickel plating is to raising AB
3type hydrogen storage alloy chemical property and cyclical stability are highly effective.
Summary of the invention
The object of this invention is to provide a kind of AB
3type Mm
0.78mg
0.22ni
2.48mn
0.09al
0.23co
0.47the nickel plating method of modifying of hydrogen bearing alloy.
Thinking of the present invention: use the method for chemical nickel plating to AB
3type Mm
0.78mg
0.22ni
2.48mn
0.09al
0.23co
0.47(Mm is mishmetal, and the percentage by weight of composition is: 82.3% La and 17.7% Nd) hydrogen bearing alloy carries out surface modification, to improve its chemical property, makes it can better be applied in Ni/MH battery.
Concrete steps are:
(1) take the raw metal of purity more than 99% according to target product mol ratio, under argon shield, prepare AB by vacuum induction melting method
3type Mm
0.78mg
0.22ni
2.48mn
0.09al
0.23co
0.47precursor alloy, alloy pig, by after mechanical crushing, with the rotating speed ball milling 60 ~ 90 minutes of 250 ~ 300 revs/min on planetary ball mill, sieves out 200 ~ 300 object Mm
0.78mg
0.22ni
2.48mn
0.09al
0.23co
0.47alloying pellet powder is for subsequent use; Described Mm is mishmetal, and the percentage by weight of composition is: 82.3% La and 17.7% Nd.
(2) Mm that 2 grams of steps (1) are obtained is got
0.78mg
0.22ni
2.48mn
0.09al
0.23co
0.47alloying pellet powder puts into 200 milliliters of plating solutions, stirs 5 minutes, adds the NaBH of 50 milliliters of 0.01 ~ 0.04mol/L
4solution, continues stirring 20 minutes, filters, and with deionized water and absolute ethanol washing, and then vacuum drying 6 ~ 10 hours at 60 DEG C, obtains the AB of plating nickel on surface
3type modified alloy, namely completes AB
3the nickel plating modification of type hydrogen storage alloy; Containing 0.6 × 10 in described plating solution
-2~ 2.4 × 10
-2the NiCl of mol/L
2with 0.5 × 10
-3~ 2.0 × 10
-3the HCl of mol/L.
The inventive method does not change the structure of precursor alloy by chemical nickel plating, modified alloy is still by LaNi
5phase and La
2ni
7phase composition, improves cyclical stability and the dynamic performance of alloy electrode, is of great practical significance to the development of Ni/MH battery.
Detailed description of the invention
embodiment 1:
(1) take the raw metal of purity more than 99% according to target product mol ratio, under argon shield, prepare AB by vacuum induction melting method
3type Mm
0.78mg
0.22ni
2.48mn
0.09al
0.23co
0.47precursor alloy, alloy pig, by after mechanical crushing, with the rotating speed ball milling 80 minutes of 260 revs/min on planetary ball mill, sieves out 280 object Mm
0.78mg
0.22ni
2.48mn
0.09al
0.23co
0.47alloying pellet powder is for subsequent use; Described Mm is mishmetal, and the percentage by weight of composition is: 82.3% La and 17.7% Nd.
(2) Mm that 2 grams of steps (1) are obtained is got
0.78mg
0.22ni
2.48mn
0.09al
0.23co
0.47alloying pellet powder puts into 200 milliliters of plating solutions, stirs 5 minutes, adds the NaBH of 50 milliliters of 0.01mol/L
4solution, continues stirring 20 minutes, filters, and with deionized water and absolute ethanol washing, and then vacuum drying 8 hours at 60 DEG C, obtains the AB of plating nickel on surface
3type modified alloy Ni-1; Containing 0.6 × 10 in described plating solution
-2the NiCl of mol/L
2with 0.5 × 10
-3the HCl of mol/L.
embodiment 2:
(1) take the raw metal of purity more than 99% according to target product mol ratio, under argon shield, prepare AB by vacuum induction melting method
3type Mm
0.78mg
0.22ni
2.48mn
0.09al
0.23co
0.47precursor alloy, alloy pig, by after mechanical crushing, with the rotating speed ball milling 80 minutes of 260 revs/min on planetary ball mill, sieves out 280 object Mm
0.78mg
0.22ni
2.48mn
0.09al
0.23co
0.47alloying pellet powder is for subsequent use; Described Mm is mishmetal, and the percentage by weight of composition is: 82.3% La and 17.7% Nd.
(2) Mm that 2 grams of steps (1) are obtained is got
0.78mg
0.22ni
2.48mn
0.09al
0.23co
0.47alloying pellet powder puts into 200 milliliters of plating solutions, stirs 5 minutes, adds the NaBH of 50 milliliters of 0.02mol/L
4solution, continues stirring 20 minutes, filters, and with deionized water and absolute ethanol washing, and then vacuum drying 8 hours at 60 DEG C, obtains the AB of plating nickel on surface
3type modified alloy Ni-2; Containing 1.2 × 10 in described plating solution
-2the NiCl of mol/L
2with 1.0 × 10
-3the HCl of mol/L.
embodiment 3:
(1) take the raw metal of purity more than 99% according to target product mol ratio, under argon shield, prepare AB by vacuum induction melting method
3type Mm
0.78mg
0.22ni
2.48mn
0.09al
0.23co
0.47precursor alloy, alloy pig, by after mechanical crushing, with the rotating speed ball milling 80 minutes of 260 revs/min on planetary ball mill, sieves out 280 object Mm
0.78mg
0.22ni
2.48mn
0.09al
0.23co
0.47alloying pellet powder is for subsequent use; Described Mm is mishmetal, and the percentage by weight of composition is: 82.3% La and 17.7% Nd.
(2) Mm that 2 grams of steps (1) are obtained is got
0.78mg
0.22ni
2.48mn
0.09al
0.23co
0.47alloying pellet powder puts into 200 milliliters of plating solutions, stirs 5 minutes, adds the NaBH of 50 milliliters of 0.04mol/L
4solution, continues stirring 20 minutes, filters, and with deionized water and absolute ethanol washing, and then vacuum drying 8 hours at 60 DEG C, obtains the AB of plating nickel on surface
3type modified alloy Ni-3; Containing 2.4 × 10 in described plating solution
-2the NiCl of mol/L
2with 2.0 × 10
-3the HCl of mol/L.
The AB obtained by above-mentioned 3 embodiments
3type modified alloy Ni-1, Ni-2 or Ni-3 are prepared as Electrode Negative sheet: get 0.1 gram of Ni-1, Ni-2 or Ni-3, add carbonyl nickel powder by weight 1:2 to mix, mixed-powder is pressed into the small pieces that diameter is 11.5 millimeters with the pressure of 10MPa by desk-top tablet press machine, then use two panels nickel foam that electrode slice is coated, adopt the pressure compaction of 10MPa to be prepared into negative plate, calculate the real content of alloyed powder sample.
Measure the phase structure of alloy, cyclical stability and dynamic performance respectively with LAND 5.3B battery test system, XRD diffractometer and CHI660E electrochemical workstation, result is as follows:
A. the maximum discharge capacity of alloy electrode is from 292.3mAh/g (AB
3) be increased to 327.7mAh/g (Ni-1), be then reduced to 298.7mAh/g(Ni-3 again).
B. after Nickel Plating Treatment, the cyclical stability of alloy electrode is improved significantly, and after 50 circulations, the circulation volume conservation rate of electrode is from 83.3% (AB
3) be increased to 94.6% (Ni-3).
C. the exchange current density of electrode, limiting current density, corrosion potential and electro-chemical activity are obtained for increase.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410299108.5A CN104226985B (en) | 2014-06-29 | 2014-06-29 | A kind of AB 3the nickel plating method of modifying of type hydrogen storage alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410299108.5A CN104226985B (en) | 2014-06-29 | 2014-06-29 | A kind of AB 3the nickel plating method of modifying of type hydrogen storage alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104226985A true CN104226985A (en) | 2014-12-24 |
| CN104226985B CN104226985B (en) | 2016-04-06 |
Family
ID=52216385
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410299108.5A Active CN104226985B (en) | 2014-06-29 | 2014-06-29 | A kind of AB 3the nickel plating method of modifying of type hydrogen storage alloy |
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| Country | Link |
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| CN (1) | CN104226985B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104862514A (en) * | 2015-05-17 | 2015-08-26 | 桂林理工大学 | A kind of surface modification method of AB3 type hydrogen storage alloy |
| CN108465820A (en) * | 2018-03-31 | 2018-08-31 | 桂林理工大学 | It is a kind of to be modified AB using Electron structure3The method of type hydrogen storage alloy |
| CN108539155A (en) * | 2018-03-31 | 2018-09-14 | 桂林理工大学 | It is a kind of to be modified AB using polyparaphenylene3The method of type hydrogen storage alloy |
| CN114122420A (en) * | 2021-03-24 | 2022-03-01 | 包头稀土研究院 | Method for making anode of direct sodium borohydride fuel cell |
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| US20040199019A1 (en) * | 2003-04-07 | 2004-10-07 | Schmidt Stephen Raymond | Nickel and cobalt plated sponge catalysts |
| CN101041180A (en) * | 2007-04-28 | 2007-09-26 | 北京有色金属研究总院 | Nanometer Al contained Ni and the preparing method |
| CN102205412A (en) * | 2011-05-06 | 2011-10-05 | 桂林理工大学 | Method of Fluorination Treatment Modification of MlNi3.5Co0.6Mn0.4Al0.5 Hydrogen Storage Alloy |
| CN102330079A (en) * | 2010-07-12 | 2012-01-25 | 惠州泰科立集团股份有限公司 | Method for treating aluminum lug |
| CN103103509A (en) * | 2013-03-07 | 2013-05-15 | 桂林理工大学 | Method for Thermoalkali Electroless Nickel Plating of Type AB3 Hydrogen Storage Alloys |
| CN103111616A (en) * | 2013-03-07 | 2013-05-22 | 桂林理工大学 | Method for carrying out fluorination modification to AB3 type hydrogen storage alloy |
| CN103611930A (en) * | 2013-12-19 | 2014-03-05 | 桂林理工大学 | A method for surface modification of AB3 type hydrogen storage alloy |
-
2014
- 2014-06-29 CN CN201410299108.5A patent/CN104226985B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040199019A1 (en) * | 2003-04-07 | 2004-10-07 | Schmidt Stephen Raymond | Nickel and cobalt plated sponge catalysts |
| CN101041180A (en) * | 2007-04-28 | 2007-09-26 | 北京有色金属研究总院 | Nanometer Al contained Ni and the preparing method |
| CN102330079A (en) * | 2010-07-12 | 2012-01-25 | 惠州泰科立集团股份有限公司 | Method for treating aluminum lug |
| CN102205412A (en) * | 2011-05-06 | 2011-10-05 | 桂林理工大学 | Method of Fluorination Treatment Modification of MlNi3.5Co0.6Mn0.4Al0.5 Hydrogen Storage Alloy |
| CN103103509A (en) * | 2013-03-07 | 2013-05-15 | 桂林理工大学 | Method for Thermoalkali Electroless Nickel Plating of Type AB3 Hydrogen Storage Alloys |
| CN103111616A (en) * | 2013-03-07 | 2013-05-22 | 桂林理工大学 | Method for carrying out fluorination modification to AB3 type hydrogen storage alloy |
| CN103611930A (en) * | 2013-12-19 | 2014-03-05 | 桂林理工大学 | A method for surface modification of AB3 type hydrogen storage alloy |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104862514A (en) * | 2015-05-17 | 2015-08-26 | 桂林理工大学 | A kind of surface modification method of AB3 type hydrogen storage alloy |
| CN108465820A (en) * | 2018-03-31 | 2018-08-31 | 桂林理工大学 | It is a kind of to be modified AB using Electron structure3The method of type hydrogen storage alloy |
| CN108539155A (en) * | 2018-03-31 | 2018-09-14 | 桂林理工大学 | It is a kind of to be modified AB using polyparaphenylene3The method of type hydrogen storage alloy |
| CN114122420A (en) * | 2021-03-24 | 2022-03-01 | 包头稀土研究院 | Method for making anode of direct sodium borohydride fuel cell |
| CN114122420B (en) * | 2021-03-24 | 2023-12-12 | 包头稀土研究院 | Method for manufacturing anode of direct sodium borohydride fuel cell |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104226985B (en) | 2016-04-06 |
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Application publication date: 20141224 Assignee: Guilin Qingjiang Construction Engineering Co.,Ltd. Assignor: GUILIN University OF TECHNOLOGY Contract record no.: X2023980044223 Denomination of invention: A Nickel Plating Modification Method for AB3Hydrogen Storage Alloy Granted publication date: 20160406 License type: Common License Record date: 20231024 |
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