CN100508252C - Carbon nanometer composite nickel-hydrogen power battery cathode sheet preparation method and its uses - Google Patents
Carbon nanometer composite nickel-hydrogen power battery cathode sheet preparation method and its uses Download PDFInfo
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- CN100508252C CN100508252C CNB2007100302637A CN200710030263A CN100508252C CN 100508252 C CN100508252 C CN 100508252C CN B2007100302637 A CNB2007100302637 A CN B2007100302637A CN 200710030263 A CN200710030263 A CN 200710030263A CN 100508252 C CN100508252 C CN 100508252C
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- tube
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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
Abstract
The method comprises: making the mechanical ball milling for the carbon nano-tube treated by mix-acid reflux purification and argon heat-treat and the LANi5 hydrogen storage metal; then adding nickel powder and evenly stirring up them; adding binder (carboxymethyl cellulose) and tetraphene emulsion to make a past form coating; evenly spreading the coating on the foam nickel to get the cathode pole piece; applying the cathode pole piece into carbon nanometer composite nickel-hydrogen battery.
Description
Technical field
The invention belongs to the Ni-MH power cell preparing technical field, be specifically related to a kind of preparation method and application thereof of carbon nanometer composite nickel-hydrogen power battery cathode sheet.
Background technology
Carbon nano-tube is with its distinctive accurate one dimension tubular structure, high electrochemical hydrogen storage capacity, and stronger oxidation resistance, the negative material that can be used as battery is applied in the secondary cell technology of preparing.The nano combined Ni-MH power cell of carbon is to add carbon nano-tube in the cell negative electrode material a kind of novel nickel-hydrogen electrokinetic cell, the high-multiplying power discharge efficient of carbon nano-tube is more superior, Ni-MH battery cycle life under the high power charging-discharging condition is poor, yet after carbon nano-tube joined Ni-MH power cell, can improve the high magnification cyclical stability of Ni-MH power cell, discharge platform voltage and heavy-current discharge performance.Therefore the nano combined Ni-MH power cell of carbon is at capacity, and there is remarkable advantages aspects such as charge-discharge performance and cycle life, have vast potential for future development at electric tool and electric automobile field.
Summary of the invention
First purpose of the present invention provides the preparation method of a kind of cathode pole piece that mixes with carbon nano-tube with higher electrochemical hydrogen storage performance and hydrogen bearing alloy.
Second purpose of the present invention provides this cathode pole piece is used to prepare the compound Ni-MH power cell of carbon nano-tube.
Technical scheme of the present invention is:
1. the making of the nano combined nickel-hydrogen battery negative pole pole piece of carbon:
(1) be 20～40nm carbon nano-tube with diameter, through mixed acid process (volume ratio of the concentrated sulfuric acid and red fuming nitric acid (RFNA) is 1～1.5:2.5～3.5) carry out purifying, and under argon gas atmosphere 700～900 ℃ of heat treatment 2h.
(2) with carbon nano-tube after above purifying and the heat treatment and LaNi
5Hydrogen bearing alloy adopts the vacuum ball-milling method to mix, and concrete operations are that rotational speed of ball-mill is 430r/min with the mixed-powder of carbon nano-tube and hydrogen bearing alloy mechanical ball milling 8h in a vacuum, and ratio of grinding media to material is 50:1, at carbon nano-tube and LaNi
5Add in the mixed-powder of hydrogen bearing alloy and add binding agent HPMC and SBR after an amount of Ni powder stirs again and add an amount of water and be modulated into paste coating, the mass ratio of above material is: hydrogen bearing alloy: carbon nano-tube: Ni powder: HPMC:SBR=100:0.1～1.0:0.5:15:2～3.
(3) will more than the paste coating for preparing be coated in equably on the nickel foam, earlier through drying at room temperature 24h, be pressed into the thickness that needs under the pressure at 11MPa more then, through cutting out, deburring, finally make cathode pole piece.
(4) the cathode pole piece surface that makes is even, and it is of a size of (315-320) mm * (35.4) mm * (0.3) mm, increases weight to be (17.0 ± 0.2) g/ sheet.On the pole piece on the given size, can carry a certain amount of active material, guarantee to be applied to make and also improved its heavy-current discharge performance when battery has high capacity behind the ni-mh sealed battery.
2. the application of the nano combined nickel-hydrogen battery negative pole pole piece of carbon:
The above cathode pole piece of making is applied to make the nano combined Ni-MH power cell of carbon, and the SC type Ni-MH power cell that makes according to SC type battery making flow process has higher capacity, better cyclical stability and better heavy-current discharge performance.
The invention has the beneficial effects as follows:
A certain amount of active material evenly can be carried on the pole piece in the cathode pole piece that makes surface, and assurance is applied to make and has also improved its heavy-current discharge performance when battery has high capacity behind the ni-mh sealed battery.
The nano combined Ni-MH power cell of prepared carbon has high capacity, good high rate during charging-discharging and good cycle life performance.Can be used for fields such as electric tool, electric motor car.
Embodiment
Embodiment 1
With diameter is carbon nano-tube employing mixed acid process (volume ratio of the concentrated sulfuric acid and red fuming nitric acid (RFNA) the is 1:2.8) purifying of 20～40nm, through adding in the negative material after 750 ℃ of heat treatments, prepares cathode pole piece according to above-mentioned preparation method again.Wherein the proportioning of negative material is: hydrogen bearing alloy: carbon nano-tube: Ni powder: HPMC:SBR=100:1.0:0.5:15:2.5,, again according to the preparation section of SC Ni-MH battery, the SC Ni-MH power cell The performance test results that makes is:
| Test condition | Capacity C (mAh) | Energy W (Wh) | Energy density (Wh/L) | Power P (W) | Specific power (W/kg) | Power density (W/L) | Cycle life | Discharge platform V |
| 0.1C filling 0.2C puts | 3369 | 4.312 | 263.75 | 0.7679 | 12.79 | 46.96 | 80%DOD 589 times | 1.25 |
| 1C fills 5C to be put | 3257.5 | 3.808 | 232.91 | 17.53 | 292.17 | 1072.17 | 70%DOD 130 times | 1.14 |
| 1C fills 10C to be put | 3135 | 3.269 | 200.00 | 31.28 | 521.37 | 1913.4 | 70%DOD 97 times | 1.05 |
Embodiment 2
With diameter is carbon nano-tube employing mixed acid process (volume ratio of the concentrated sulfuric acid and red fuming nitric acid (RFNA) is 1.5: the 3.3) purifying of 20～40nm, through adding in the negative material after 800 ℃ of heat treatments, prepares cathode pole piece according to above-mentioned preparation method again.Wherein the proportioning of negative material is: hydrogen bearing alloy: carbon nano-tube: Ni powder: HPMC:SBR=100:0.8:0.5:15:2.2,, again according to the preparation section of SC Ni-MH battery, the SC Ni-MH power cell The performance test results that makes is:
| Test condition | Capacity C (mA h) | Energy W (Wh) | Energy density (Wh/L) | Power P (W) | Specific power (W/kg) | Power density (W/L) | Cycle life | Discharge platform V |
| 0.1C filling 0.2C puts | 3459 | 4.372 | 267.4 | 0.758 3 | 12.63 | 46.37 | 80%DO D 687 times | 1.29 |
| 1C fills 5C to be put | 3357.5 | 3.864 | 236.4 | 17.26 | 287.70 | 1055.65 | 70%DO D 230 times | 1.16 |
| 1C fills 10C to be put | 3165 | 3.272 | 200.2 | 31.01 | 516.90 | 1896.08 | 70%DO D 187 times | 1.04 |
Embodiment 3
With diameter is carbon nano-tube employing mixed acid process (volume ratio of the concentrated sulfuric acid and red fuming nitric acid (RFNA) is 1: the 3) purifying of 20～40nm, through adding in the negative material after 850 ℃ of heat treatments, prepares cathode pole piece according to above-mentioned preparation method again.Wherein the proportioning of negative material is: hydrogen bearing alloy: carbon nano-tube: Ni powder: HPMC:SBR=100:0.5:0.5:15:2.6,, again according to the preparation section of SC Ni-MH battery, the SC Ni-MH power cell The performance test results that makes is:
| Test condition | Capacity C (mAh) | Energy W (Wh) | Energy density (Wh/L) | Power P (W) | Specific power (W/kg) | Power density (W/L) | Cycle life | Discharge platform V |
| 0.1C filling 0.2C puts | 3385.7 | 4.32 | 264.2 | 0.7656 | 12.76 | 46.83 | 80%DO D 611 times | 1.28 |
| 1C fills 5C to be put | 3242.5 | 3.79 | 231.8 | 17.53 | 292.2 | 1072.35 | 70%DO D 202 times | 1.16 |
| 1C fills 10C to be put | 3215 | 3.37 | 206.1 | 31.44 | 523.9 | 1922.75 | 70%DO D 151 times | 1.04 |
Embodiment 4
With diameter is carbon nano-tube employing mixed acid process (volume ratio of the concentrated sulfuric acid and red fuming nitric acid (RFNA) the is 1.2:3.3) purifying of 20～40nm, through adding in the negative material after 900 ℃ of heat treatments, prepares cathode pole piece according to above-mentioned preparation method again.Wherein the proportioning of negative material is: hydrogen bearing alloy: carbon nano-tube: Ni powder: HPMC:SBR=100:0.1:0.5:15:2.8,, again according to the preparation section of SC Ni-MH battery, the SC Ni-MH power cell The performance test results that makes is:
| Test condition | Capacity C (mAh) | Energy W (Wh) | Energy density (Wh/L) | Power P (W) | Specific power (W/kg) | Power density (W/L) | Cycle life | Discharge platform V |
| 0.1C filling 0.2C puts | 3399.3 | 4.337 | 265.3 | 0.7655 | 12.75 | 46.82 | 80%DO D 601 times | 1.27 |
| 1C fills 5C to be put | 3250 | 3.757 | 229.8 | 17.34 | 289.00 | 1060.55 | 70%DO D 127 times | 1.15 |
| 1C fills 10C to be put | 3200 | 3.331 | 203.7 | 31.23 | 520.47 | 1910.09 | 70%DO D 90 times | 1.02 |
Embodiment 5
The cathode pole piece that makes is made the nano combined Ni-MH power cell of carbon according to the preparation method of SC type ni-mh, and concrete operations are:
(1) making of anode pole piece: with Ni (OH)
2: CoO:Y
2O
3Mix respectively through 100 orders and 150 purpose sieves according to 92:7:1, add an amount of adhesive (20% PTFE), mix, add 90 ℃ deionized water, stir 2h, leave standstill 10h and be mixed with.With the even scrubbing brush of brush on the collector nickel foam, directly dry-pressing and be cut into the positive plate of desired thickness.
Wherein: the positive plate size is 270 * 34 * 0.5mm mm, and the electrolyte injection rate is (5.0 ± 0.05) g/ sheet, and box hat is of a size of Φ 22.2/21.2 * 43.0mm. and is prepared into SC type Ni-MH power cell, and above-mentioned electrolyte adopts binary alkali lye: KOH:LiOH:H
2O=34:1.6:66.
(3) above battery is changed into according to following process high-temperature, actual conditions is:
1. the 0.1C charging is 2 hours, shelves 24 hours for 45 ℃, and normal temperature was shelved 4 hours,
2. under 20 ℃, 0.1C charging 100 minutes, 0.5C discharge 100 minutes 0.2C are again put to 1V,
3. under 20 ℃, 0.3C charging 2 hours, 0.5C is put to 1V,
4. the 0.5C charging is 2 hours.
The nano combined Ni-MH power cell of the carbon that makes has high capacity, and good high rate during charging-discharging and good cycle life performance can be used for fields such as electric tool, electric motor car.
Claims (3)
1. the preparation method of a carbon nanometer composite nickel-hydrogen power battery cathode sheet has following steps:
(1) be 20～40nm carbon nano-tube with diameter, carry out purifying through mixed acid process, wherein the volume ratio of the concentrated sulfuric acid and red fuming nitric acid (RFNA) is 1～1.5: 2.5～3.5, and 700～900 ℃ of heat treatment 2 hours under argon gas atmosphere;
(2) with carbon nano-tube after above purifying and the heat treatment and hydrogen bearing alloy LaNi
5An amount of nickel powder of adding stirs after adopting vacuum ball-milling method mechanical ball milling, adds an amount of water of binding agent HPMC and SBR interpolation again and is modulated into paste coating, and the mass ratio of above material is: hydrogen bearing alloy LaNi
5: carbon nano-tube: Ni powder: HPMC: SBR=100: 0.1～1.0: 0.5: 15: 2～3;
(3) paste coating for preparing more than the general is coated on the nickel foam equably, and the process drying at room temperature is 24 hours earlier, is pressed into cathode pole piece then under the pressure of 11MPa.
2. preparation method according to claim 1, with the mixed-powder of above-mentioned carbon nano-tube and hydrogen bearing alloy mechanical ball milling 8 hours in a vacuum, rotational speed of ball-mill is 430r/min in the above-mentioned steps (2), ratio of grinding media to material is 50: 1.
3. the application of a carbon nanometer composite nickel-hydrogen power battery cathode sheet is characterized in that: the cathode pole piece that preparation method according to claim 1 is made is applied to make the nano combined Ni-MH power cell of carbon.
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| CNB2007100302637A CN100508252C (en) | 2007-09-17 | 2007-09-17 | Carbon nanometer composite nickel-hydrogen power battery cathode sheet preparation method and its uses |
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| CNB2007100302637A CN100508252C (en) | 2007-09-17 | 2007-09-17 | Carbon nanometer composite nickel-hydrogen power battery cathode sheet preparation method and its uses |
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| CN100508252C true CN100508252C (en) | 2009-07-01 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102593437B (en) * | 2012-02-29 | 2014-08-06 | 上海交通大学 | Disposable nickel hydrogen battery negative electrode material, negative electrode piece, battery and preparation methods thereof |
| CN102779981B (en) * | 2012-08-01 | 2014-06-25 | 广州市云通磁电有限公司 | Preparation method of negative electrode plate of nickel-metal hydride battery |
| CN102820457A (en) * | 2012-08-30 | 2012-12-12 | 上海锦众信息科技有限公司 | Preparation method of negative pole of power battery |
| CN103253648B (en) * | 2012-11-13 | 2015-04-22 | 山东省科学院新材料研究所 | Preparation method of carbon nanotube by growing on foamed nickel substrate |
| CN103682264A (en) * | 2013-12-11 | 2014-03-26 | 高建军 | Preparation method of cathode plate of nickel-metal hydride battery |
| CN104617282B (en) * | 2015-02-16 | 2017-03-15 | 徐象华 | A kind of manufacture method of Ni-based high-energy secondary battery cathode size |
| CN105742578B (en) * | 2016-03-22 | 2018-11-13 | 中国科学院理化技术研究所 | A kind of nickel-hydrogen battery negative pole slurry preparation method of addition carbon nanotube |
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Non-Patent Citations (4)
| Title |
|---|
| 碳纳米管的电化学储氢性能研究. 付小娟.广东工业大学学位论文. 2005 |
| 碳纳米管的电化学储氢性能研究. 付小娟.广东工业大学学位论文. 2005 * |
| 纳米添加剂的制备及其在MH/Ni电池中的应用. 黄行康.浙江工业大学硕士学位论文. 2003 |
| 纳米添加剂的制备及其在MH/Ni电池中的应用. 黄行康.浙江工业大学硕士学位论文. 2003 * |
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