CN100449828C - Titanium base foam lead positive and negative electrode plate grating material for lead acid accumulator and its producing method - Google Patents
Titanium base foam lead positive and negative electrode plate grating material for lead acid accumulator and its producing method Download PDFInfo
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- CN100449828C CN100449828C CNB2006101102347A CN200610110234A CN100449828C CN 100449828 C CN100449828 C CN 100449828C CN B2006101102347 A CNB2006101102347 A CN B2006101102347A CN 200610110234 A CN200610110234 A CN 200610110234A CN 100449828 C CN100449828 C CN 100449828C
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- pedestal
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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
This invention discloses a positive and negative plate grid matrial of Ti-base foam lead of lead-acid storage cells, which takes tubular crystals made of Ti or Ti alloy and foam Ti with three-D net structure as the pedestal to plate PbO2 or pure Pb on the pedestal. The preparation method includes: 1, taking TiCl4 and Mg as the raw material, and Mg reduces Ti in TiCl4 in a reduction furnace to be vacuum distilled and condensed to form foam Ti, 2, cutting the Ti foam to mold, 3, eliminating passivation films on the shaped foam Ti to activate it, 4, plating a high conductive layer on the surface of the foam Ti, 5, heat-processing the pedestal, 6, plating PbO2 on the pedestal to get a positive plate grid material or plating pure Pb to get a negative plate grid material.
Description
Technical field
The present invention is relevant with the electrode of storage battery, and is special relevant with the lead-acid battery electrode carrier material, also relevant with the manufacture method of carrier.
Background technology
As everyone knows, lead acid accumulator is with its good performance and comprehensive advantage, dominating world's storage battery industry, at aspects such as electric automobile, hybrid vehicle, wind power generation, solar cell and electrical thermal storage batteries, lead acid accumulator is still classified first-selected power supply and irreplaceable power-supply battery as.Yet there is big, the Heavy Weight of many deficiencies, particularly volume in lead acid accumulator itself, and active material is efficient low, and gravimetric specific energy low (average 30-40Wh/kg) is the deficiency and the shortcoming of its maximum.In order to improve the performance of lead acid accumulator, start with from grid material and battery structure aspect in countries in the world, invent some novel grid materials such as copper pull mesh grid, plumbous cloth etc. in succession, its gravimetric specific energy can be brought up to 50Wh/kg, these achievements in research push forward the lead-acid battery performance, but increasing degree is limited, can not satisfy requirement high-power, high-energy-density.In recent years, the research of China's lead-acid battery has had bigger progress, obtaining many achievements aspect the battery electrode grid material, for example No. 96110730.8 " manufacture method of foamed lead plate for negative pole of lead-acid accumulator ", No. 03132621.8 " lead-acid battery hot-dip foam stereotype grid and preparation method thereof " of Chinese patent, No. 200510127392.9 " coiled lead-acid battery with lead foam negative electrode grid and preparation methods " etc.These methods all have the effect that increases the storage battery specific energy, have improved 30% with traditional grid comparison specific energy, use but these materials only limit to negative pole, can't be used for positive pole; Also exist copper all problems such as to separate out simultaneously, be difficult to practical application.
Summary of the invention
The objective of the invention is to by preferred definite lead-acid battery optimum electrode grid metallic element, research and develop a kind of lead acid accumulator titanium foam base positive/negative plate grid material, big from basic solution lead-acid battery weight, active material is efficient low, the crucial difficult problem that specific energy is little.
Another purpose of the present invention is to provide the manufacture method of above-mentioned lead acid accumulator titanium foam base positive/negative plate grid material, it is had satisfy the performance that electric automobile, energy storage battery etc. require high-energy-density, large power supply.
The inventor points out: in lead-acid battery, anodal condition of work is very special, therefore the specification requirement of anode plate grid material is very harsh, improve the lead-acid battery specific energy, and key is the correct anodal metallic element and the version and the function of grid material selected.The inventor determines that by preferred titanium is a lead-acid battery optimum electrode grid metallic element.Titanium is the metal with performance as the mystery, and its weight has only half of iron and steel, but specific strength then is one times of iron and steel, is five times of fine aluminium; Its mechanical strength is big, and plasticity is good, acid-fast alkali-proof, and corrosion stability is strong, and is high temperature resistant, anti-ultralow temperature, the nonmagnetic premium properties that waits can satisfy the specification requirement of lead-acid battery electrode plate grid material fully.
It is titanium that the inventor determines anodal metallic element by long-term repetition test, invented the tubular crystals made from titanium or titanium alloy, the titanium foam with tridimensional network is a pedestal, on this pedestal, electroplate brown lead oxide or pure lead, resulting novel lead-acid storage battery positive and negative electrode plate grating material.Used titanium foam is a kind of have ultralight, high strength, high conduction, anticorrosive, high porosity, and specific area is big, fills that holding power is strong, the functional electrode material of high-efficiency energy-storage, resource-conserving, is present optimal electrode metal pedestal material;
The manufacturing lead acid accumulator titanium foam base positive/negative plate grid material method that the inventor provides comprises:
1. getting titanium tetrachloride and magnesium is raw material, and in reduction furnace, magnesium is smelted the reduction of the titanium in the titanium tetrachloride through vacuum distillation, and condensation-crystallization forms titanium foam;
2. with the titanium foam cutting forming;
3. the titanium foam that is shaped is removed passivating film and carry out activation processing;
4. at the high conductive layer of titanium foam surface plating;
5. the titanium foam pedestal that plates high conductive layer is heat-treated;
6. the plating brown lead oxide obtains titanium foam base anode plate grid material on pedestal, or plates pure lead and obtain titanium foam base negative grid material.
In the first step of said process, described titanium foam is the foam metal that tubular crystals has tridimensional network, and its structural material technical indicator is: porosity 〉=80%; The more traditional lead alloy grid of weight reduces by 90%; Surface density≤1000g/m
2The more traditional lead alloy grid of specific area increases 10-20 doubly.
In second step of said process, the cutting of titanium foam adopts the digital control wire-electrode cutting technology to carry out.
In the 3rd step of said process, the activation processing of described titanium foam is by corrosion-tank finishing process titanium surface passivated membrane (oxide-film) to be removed under vacuum condition, plates active membrane then, improves the affinity of titanium base and coating.
In the 4th step of said process, make titanium foam obtain high conductive layer at surface plating fine silver or argentalium alloy.
In above-mentioned the 5th step, the heat treatment of titanium foam pedestal is carried out in electric furnace, and for silver-plated titanium foam pedestal, heat treatment temperature is 600-800 ℃, and for the titanium foam pedestal of silver-plated lead alloy, heat treatment temperature is 170～220 ℃.
The inventor points out that titanium is a kind of valve metal, and the surface forms one deck passivating film densification, that chemical stability is high (oxide-film) under normal conditions, therefore must and carry out activation processing with its removal, plates high conductive layer then on the surface and just can make grid material; High conductive coating is good with silver, in order to reduce cost, also can electroplate 8%～15% argentalium alloy; The purpose that the titanium foam pedestal is heat-treated is to make the combination of titanium, silver, lead metal more tight.
Electrode technology index by this method manufacturing is: the more traditional lead alloy battery lead plate of weight reduces by 60%～80%; Active material is efficient to be 50%～90%; The more traditional lead alloy electrode of gravimetric specific energy improves 1～2 times, reaches 70～100Wh/kg.
The positive and negative grid material of lead acid accumulator provided by the invention and traditional lead alloy grid compare, and weight has only 1/10～1/20 of traditional grid, and behind the filling active material, electrode weight has only 1/2～1/3 of traditional electrode.Active material is efficient can bring up to 60%～90% from traditional 10%～50%, and gravimetric specific energy is brought up to 70～100Wh/kg from 30 traditional～40Wh/kg, even can reach 120Wh/kg.Along with the significantly raising of specific energy, this novel lead-acid battery made from the titanium foam pedestal will can satisfy the needs of accumulation of energys such as high-power Vehicular battery and power plant, hydroelectric station, wind energy, solar energy fully.
Description of drawings
Fig. 1 is titanium foam three-dimensional structure material electronics probe scanning figure provided by the invention.Fig. 2 is the positive and negative grid material manufacture method of a lead acid accumulator titanium foam base provided by the invention block diagram.
Embodiment
Embodiment 1: getting titanium tetrachloride and magnesium is raw material, and in reduction furnace, magnesium is with the reduction of the titanium in the titanium tetrachloride, and its reaction temperature is 750 ℃; Pass through vacuum distillation again, vacuum degree is 0.1333～0.0013Pa (10
-3～10
-5The mmHg post), vapo(u)rizing temperature is 950～1000 ℃, and condensation-crystallization forms the titanium foam with tridimensional network of tubulose; Adopt the electricity cutting technology with the titanium foam cutting forming; The titanium foam that is shaped is removed passivating film and carried out activation processing, promptly under vacuum condition, titanium surface passivated membrane (oxide-film) is removed, plate active membrane then by corrosion-tank finishing process; Afterwards at titanium foam surface plating fine silver; In electric furnace the titanium foam pedestal that plates high conductive layer is heat-treated, heat treatment is that temperature is handled 10min down for 700 ℃; On pedestal, plate brown lead oxide, obtain the anode plate grid material; Plate pure lead, obtain negative grid material.
Embodiment 2: getting titanium tetrachloride and magnesium metal is raw material, and in reduction furnace, magnesium is with the reduction of the titanium in the titanium tetrachloride, and reaction temperature is 750 ℃; Through vacuum distillation, vacuum degree is 0.1333～0.0013Pa (10
-3～10
-5The mmHg post), condensation-crystallization forms the titanium foam with tridimensional network of tubulose; Adopt the digital control wire-electrode cutting technology with the titanium foam cutting forming again; The titanium foam that is shaped is removed passivating film and carried out activation processing, promptly under vacuum condition, titanium surface passivated membrane (oxide-film) is removed, plate active membrane then by corrosion-tank finishing process; Plate the argentalium alloy of argentiferous 11% afterwards on the titanium foam surface; In electric furnace the titanium foam pedestal that plates high conductive materials is heat-treated, heat treatment temperature is 200 ℃; On pedestal, plate brown lead oxide, obtain the anode plate grid material; Plate pure lead, obtain negative grid material.
Claims (7)
1 lead acid accumulator titanium foam base positive and negative electrode plate grating material, it is characterized in that this material is that the titanium foam of the tridimensional network made with titanium or titanium alloy is a pedestal, on this pedestal, electroplate brown lead oxide or pure lead, resulting lead acid accumulator positive and negative electrode plate grating material.
2 manufacture methods according to the described material of claim 1, its feature comprises:
1. getting titanium tetrachloride and magnesium is raw material, and in reduction furnace, magnesium is smelted the reduction of the titanium in the titanium tetrachloride through vacuum distillation, and condensation-crystallization forms titanium foam;
2. with the titanium foam cutting forming;
3. the titanium foam that is shaped is removed passivating film and carry out activation processing;
4. at the high conductive layer of titanium foam surface plating;
5. the titanium foam pedestal that plates high conductive layer is heat-treated;
6. the plating brown lead oxide obtains the anode plate grid material on pedestal, or plates pure lead and obtain negative grid material.
3 manufacture methods according to claim 2 is characterized in that in the first step of described method that described titanium foam is the foam metal with tridimensional network, and its structural material technical indicator is: porosity 〉=80%; The more traditional lead alloy grid of weight reduces by 90%; Surface density≤1000g/m
2The more traditional lead alloy grid of specific area increases 10-20 doubly.
4 manufacture methods according to claim 2 is characterized in that the cutting of titanium foam adopts the digital control wire-electrode cutting technology to carry out in second step of described method.
5 manufacture methods according to claim 2 is characterized in that the activation processing of titanium foam is by corrosion-tank finishing process the titanium surface passivated membrane to be removed, and plates active membrane then in the 3rd step of described method under vacuum condition.
6 manufacture methods according to claim 2 is characterized in that described high conductive layer is fine silver layer or argentalium alloy-layer in the 4th step of described method.
7 manufacture methods according to claim 2, it is characterized in that in the 5th step of described method, the heat treatment of titanium foam pedestal is carried out in electric furnace, for silver-plated titanium foam pedestal, heat treatment temperature is 600-800 ℃, for the titanium foam pedestal of silver-plated lead alloy, heat treatment temperature is 170～220 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006101102347A CN100449828C (en) | 2006-12-29 | 2006-12-29 | Titanium base foam lead positive and negative electrode plate grating material for lead acid accumulator and its producing method |
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| CNB2006101102347A CN100449828C (en) | 2006-12-29 | 2006-12-29 | Titanium base foam lead positive and negative electrode plate grating material for lead acid accumulator and its producing method |
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| CN1988224A CN1988224A (en) | 2007-06-27 |
| CN100449828C true CN100449828C (en) | 2009-01-07 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102074702A (en) * | 2010-12-28 | 2011-05-25 | 株洲冶炼集团股份有限公司 | Lead-carbon composite material |
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| CN101877403B (en) * | 2009-09-18 | 2012-08-22 | 华南师范大学 | Manufacturing method and device of cell negative plate |
| CN101728539B (en) * | 2009-12-18 | 2012-01-04 | 西北有色金属研究院 | Lead-acid accumulator Ti-0.2Pd titanium alloy-based foamed lead negative grid |
| CN102005574B (en) * | 2010-10-29 | 2013-03-27 | 济南兄弟金属科技有限公司 | Light plate grid for lead-acid storage battery and preparation method thereof |
| CN102544600A (en) * | 2012-03-01 | 2012-07-04 | 浙江世锋新能源开发有限公司 | Titanium material capacitance battery |
| CN102903931A (en) * | 2012-10-18 | 2013-01-30 | 双登集团股份有限公司 | Lead-acid battery plate grid alloy |
| CN108258248B (en) * | 2016-12-28 | 2020-09-01 | 天能电池集团股份有限公司 | Long-life composite grid suitable for lead storage battery and preparation method thereof |
| CN108963269A (en) * | 2018-06-26 | 2018-12-07 | 江苏华富储能新技术股份有限公司 | A kind of preparation method of process for positive slab lattice of lead-acid accumulator |
| CN112159987A (en) * | 2020-09-03 | 2021-01-01 | 广东臻鼎环境科技有限公司 | Sandwich structure composite lead electrode and preparation method thereof |
| CN112095118A (en) * | 2020-09-03 | 2020-12-18 | 广东臻鼎环境科技有限公司 | Composite lead dioxide anode and preparation method thereof |
| CN113224312B (en) * | 2021-04-15 | 2022-07-29 | 淄博火炬能源有限责任公司 | Titanium/copper-based long-life high-power lead-acid storage battery and preparation method thereof |
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| CN1206937A (en) * | 1997-07-29 | 1999-02-03 | 上海兴东科技发展公司 | Porous acid-resistant alloy and fibre composite blate matrix |
| JP2005044759A (en) * | 2003-07-25 | 2005-02-17 | Furukawa Battery Co Ltd:The | Lead-acid storage battery and manufacturing method of the same |
| CN1734824A (en) * | 2004-08-12 | 2006-02-15 | 张楚楩 | Titanium aluminium power battery and production process thereof |
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- 2006-12-29 CN CNB2006101102347A patent/CN100449828C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5521029A (en) * | 1995-02-22 | 1996-05-28 | At&T Corp. | Current collecting elements |
| CN1206937A (en) * | 1997-07-29 | 1999-02-03 | 上海兴东科技发展公司 | Porous acid-resistant alloy and fibre composite blate matrix |
| JP2005044759A (en) * | 2003-07-25 | 2005-02-17 | Furukawa Battery Co Ltd:The | Lead-acid storage battery and manufacturing method of the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102074702A (en) * | 2010-12-28 | 2011-05-25 | 株洲冶炼集团股份有限公司 | Lead-carbon composite material |
| CN102074702B (en) * | 2010-12-28 | 2012-11-07 | 株洲冶炼集团股份有限公司 | Preparation method of lead-carbon composite material |
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| CN1988224A (en) | 2007-06-27 |
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