CN1591957B - High-energy all-sealed lead-acid battery without maintaining for submarine - Google Patents

High-energy all-sealed lead-acid battery without maintaining for submarine Download PDF

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CN1591957B
CN1591957B CN200410039160A CN200410039160A CN1591957B CN 1591957 B CN1591957 B CN 1591957B CN 200410039160 A CN200410039160 A CN 200410039160A CN 200410039160 A CN200410039160 A CN 200410039160A CN 1591957 B CN1591957 B CN 1591957B
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battery
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lead
powder
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CN1591957A (en
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陈有孝
陈嘉骞
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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
    • 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

Abstract

This invention put forward a new type of high energy total sealing free of maintenance lead-acid battery used in submarines which cab be entirely exchange with the current batteries, compared with the present batteries, its volume is more than a double of the present, the discharging time of 6000A increases to 3 hours from 1 hour and that of 250A increases from 50 hours to 100 hours.

Description

Submarine high-energy sealed non-maintenance lead-acid accumulator cell
Technical field: the effect in modernized war of conventional submarine and nuclear-powered submarine increases day by day, and especially modern war makes submarine become the indispensable equipment of modernized naval, also is the symbol of a national naval military strength.This project belongs to modernization of national defense field.
Background technology: well-known, lead acid accumulator is the unique power source of conventional submarine underwater operation, nuclear-powered submarine also with lead-acid battery as stand-by power supply.For this reason, the performance of lead-acid battery directly influences the performance of submarine and the fighting capacity of submarine.Submarine plays very large effect as one of important equipment of naval in naval and coast defence construction.Especially for defensive coast defence construction.The effect of conventional submarine is important especially.Because the stable performance of lead acid accumulator, discharge are steadily, especially big capacity, service behaviour such as high-power are that other secondary cell can't replace as nickel-cadmium, nickel-Hydrogenized compound, lithium ion battery.For this reason, improve the integral level of present lead acid accumulator, on the basis of satisfying submarine basic demand and absolute interchangeability, fundamentally change the structure of submarine with lead-acid battery, development and production high-energy full sealed non-maintenance submarine has very important meaning with lead-acid battery.
Summary of the invention: at present, the lead acid accumulator that conventional submarine is prepared is 2V6000Ah (discharge of 1 a hour rate) plain edition lead acid accumulator, and the volume of this lead acid accumulator is 270.4dm 3, weight is 647kg.
1 hour rate volumetric specific energy only is 44.378Wh/dm 3
20 hour rate volumetric specific energys only are 76.284Wh/dm 3
1 hour rate gravimetric specific energy only is 14.9Wh/kg;
20 hour rate gravimetric specific energies only are 25.59Wh/kg.Owing to the performance limitations of present submarine, directly influence the operational performance of submarine with lead acid accumulator.In (the 6000A discharge) only 1 hour that full speed ahead, just having to emerges charges the battery as submarine.And the lead acid accumulator that now is used for submarine is the plain edition lead acid accumulator, and this battery can produce a large amount of sulfuric acid mists in charging process, the extremely limited submarine of severe contamination space, infringement soldier health.Submarine can cause battery to spill the electrolyte heavy corrosion submarine parts of sulfuric acid in big marine jolting.And in the running of battery, the soldier will add sulfuric acid electrolyte to battery in narrow space, safeguards that its degree of difficulty is difficult to the imagination.
The present invention proposes a kind of novel high-energy full-sealed lead-acid accumulator, and the object of the present invention is achieved like this:
The positive grid alloy material of this battery is:
Pb+Ax+By+Cz+Du+Ev+Fw+Gt+Ha
Wherein: A=Ca, Sr, k x=0.001～1.0%;
B＝Na 2S 4，Na 2S 5 y＝0.001～1.0％；
C＝As，Bi z＝0.001～0.05％；
D＝Ce，Cu u＝0.001～0.3％；
E＝Mg，Al v＝0.001～0.3％；
F＝Zn，Sn w＝0.001～1.0％；
G＝In，Ag t＝0.001～0.5％；
H＝Se，Te a＝0.001～0.3％
The positive electrode active compound composition of battery is:
It is 1.08～1.25g/cm that the lead powder that per hundred kilograms of oxidizabilities are 75-78% adds density 3Sulfuric acid solution 3.7L, add different in nature graphite 300-350g, add 800-1000 order ZrO 2Powder 200-280g, add superfine metal lead powder 300-320g, add the acrylic short fiber of 200-280g, add the PTFE of 100-180g, transferring to apparent gravity with pure water is 4.25-4.3g/cm 3
The negative plate grid alloy material of this battery is:
Pb+Ax+Cz+Du+Ev+Fw
Wherein: A=Ca, Na, K, Sr x=0.001～0.5%;
C＝Zn，Sn z＝0.01～1.0％；
D＝Ag，Bi u＝0.001～0.5％；
E＝Cu，Zn v＝0.001～0.3％；
F＝Ce，S w＝0.001～0.2％
The composition of cathode active materials of battery is:
It is 1.08-1.30g/cm that the lead powder that per hundred kilograms of oxidizabilities are 75-80% adds density 3Sulfuric acid solution 3.5-3.8L, add α β naphthoic acid 600-700g, add BaSO 4600-700g adds different in nature graphite 300-350g, adds 200-300g800-1200 purpose Al 2O 3Powder adds 800-1000 purpose ZrO 2Powder 100g adds humic acid 500-600g, and transferring to the lead plaster apparent gravity with pure water is 4.15-4.25g/cm 3
Battery case adopts the ABS engineering material, adopts nylon.
Electrolyte prescription is the phosphoric acid that adds 1% percent by volume in the sulfuric acid solution of 64-65%, adds 0.08% ortho phosphorous acid disodium, adds 0.02%NaSO 4, the CaSO of adding 0.01% 4
Embodiment:
Embodiment 1:
Make the bike high energy and fully closed maintenance-free lead accumulator of 2V6000Ah (1 hour rate) submarine.
1, shell adopts the ABC engineering plastics, and shell overall dimension is 638mm * 386mm * 1098mm
2, barrier film is selected the barrier film that is used for sealed lead-acid accumulator free from maintenance that Nanjing glass fibre research institute produces for use.
3, positive plate grid size (seeing Figure of description 1-1): 558mm * 346mm * 4mm
Grid size: wide 50m, high 20m, totally four.
Negative grid size (seeing Figure of description 1-2): 558mm * 346mm * 2.5mm
Grid, the wide 50m of plate ear, high 20m, totally four.
4, the production of positive plate grid after Pb melt, adds 0.09% Ca, the Na of adding 0.05% in lead melting furnace 2S 4, the Ag of adding 0.02%, the Al of adding 0.02%, the Cu of adding 0.02%, the Sn of adding 0.2%, the Se of adding 0.01%, temperature rises to 520 ± 10 ℃, preserves moisture 15-20 minute, is cast in the anode plate grid mould, makes anode plate grid.
5, bear the production of plate grid: after Pb is melted, add 0.095% Ca in lead melting furnace, add 0.02% Cu, the Bi of adding 0.01%, the S of adding 0.01%, the Sn of adding 0.5%, temperature rises to 510 ± 10 ℃, waters in the grid mould that casts from cast iron, makes negative plate grid.
6, in closing the cream machine, add and add 0.15% acrylic short fiber behind the Pb powder, add 0.08% PTFE, add 0.08% different in nature graphite, add 0.06% ZrO 2, adding density is 1.25g/cm 3H 2SO 4Solution adds 3.7L in per hundred kilograms of Pb powder, and transferring to the lead plaster apparent gravity with pure water is 4.25g/cm 3, leave standstill after 15 minutes this lead plaster is applied to positive plate grid, make positive plate.
7, the Pb powder is put into the cream machine that closes, added 0.02% barium sulfate, add 0.21% humic acid, add 0.18% α β naphthoic acid, add 0.02% Al 2O 3, adding 0.18% acrylic short fiber, adding density is 1.25g/cm 3H 2SO 4Solution (per hundred kilograms of lead powder add 3.6L), transferring to the lead plaster apparent gravity with pure water is 4.2g/cm 3, this lead plaster is applied to volt plate grid, make negative plate.
8, positive and negative pole plate is by conventional curing, chemical synthesis technology, make ripe pole plate, 96 positive plates and 100 negative plates are divided into four groups, 24 of every group of positive plates, 25 of negative plates are in the anti-expansion set of packing into, acid-proof applies mechanically nylon or the ABS engineering plastics are made, be of a size of 526mm * 350mm * 236mm, wall thickness 2.6mm, anti-expansion set is seen Figure of description 2.
With the positive and negative pole plate anti-expansion set of packing into, 24 positive plates, 25 negative plates.Specifically see Figure of description 3.
With bus-bar plate is welded, see Figure of description 4.
With four groups of bus-bar welderings, see Figure of description 5 in the battery case of packing into.
Connect and draw 8 poles, four positive poles, four negative poles are specifically seen Figure of description 6.
Arrive battery upper casing good seal with the ABS adhesive, adding proportion is 1.30g/cm 3Electrolyte, the composition of electrolyte be sulfuric acid solution to add percent by volume be 1% phosphoric acid, add 0.08% ortho phosphorous acid disodium, add 0.02% NaSO 4, the CaSO of adding 0.01% 4
The performance index of novel battery are as follows:
Original submarine 2V6000Ah battery Novel battery
Volume (mm) 638×386×1098(270dm 3) 638×386×1098 (270dm 3)
6000A closes capacity discharge time Closed 6000Ah in 1 hour Closed 18000Ah in 3 hours
250A discharge time Closed 12500Ah in 50 hours Closed 25000Ah in 100 hours
Volumetric specific energy (1 hour rate) 44.4Wh/dm 3 133Wh/dm 3
Volumetric specific energy (50 hour rate) 92.59Wh/dm 3 185.18Wh/dm 3
Weight 647kg 800kg
Gravimetric specific energy (1 hour rate) 18.54Wh/kg 45Wh/kg
Battery types Plain edition Closed maintenance free
Description of drawings: Fig. 1-the 1st, positive plate grid; Fig. 1-2 is negative plate grid; Fig. 2 is anti-expansion set;
Fig. 3 is the anti-expansion set that 24 positive plates, 25 negative plates are housed;
Fig. 4 is a bus-bar; Fig. 5 is the battery case that 4 groups of bus-bars are housed;
Fig. 6 is the battery vertical view.

Claims (3)

1. bike high energy and fully closed lead-acid storage battery, it is characterized in that, change the method that traditional polar plate of lead acid storage battery is vertical arrangement, pole plate is kept flat, make the lug of pole plate can be positioned at the centre of grid, to obtain best catchment effect, X sheet positive plate is welded lug with bus-bar, lug is welded with bus-bar with X+1 sheet negative plate, draw solder terminal from both sides, in charge and discharge process, be out of shape for preventing pole plate, expansion causes the short circuit between pole plate, adds an anti-expansion set in battery case, will be just, the negative pole group packs into and prevents reinstalling battery case in the expansion set;
The positive grid alloy material of this battery is:
Pb+Ax+By+Cz+Du+Ev+Fw+Gt+Ha
Wherein: A=Ca, Sr, k x=0.001～1.0%;
B＝Na 2S 4，Na 2S 5 y＝0.001～1.0％；
C＝As，Bi z＝0.001～0.05％；
D＝Ce，Cu u＝0.001～0.3％；
E＝Mg，Al v＝0.001～0.3％；
F＝Zn，Sn w＝0.001～1.0％；
G＝In，Ag t＝0.001～0.5％；
H＝Se，Te a＝0.001～0.3％
The positive electrode active compound composition of battery is:
It is 1.08～1.25g/cm that the lead powder that per hundred kilograms of oxidizabilities are 75-78% adds density 3Sulfuric acid solution 3.7L, add different in nature graphite 300-350g, add 800-1000 order ZrO 2Powder 200-280g, add superfine metal lead powder 300-320g, add the acrylic short fiber of 200-280g, add the PTFE of 100-180g, transferring to apparent gravity with pure water is 4.25-4.3g/cm 3
The negative plate grid alloy material of this battery is:
Pb+Ax+Cz+Du+Ev+Fw
Wherein: A=Ca, Na, K, Sr x=0.001～0.5%;
C＝Zn，Sn z＝0.01～1.0％；
D＝Ag，Bi u＝0.001～0.5％；
E＝Cu，Zn v＝0.001～0.3％；
F＝Ce，S w＝0.001～0.2％
The composition of cathode active materials of battery is:
It is 1.08-1.30g/cm that the lead powder that per hundred kilograms of oxidizabilities are 75-80% adds density 3Sulfuric acid solution 3.5-3.8L, add α β naphthoic acid 600-700g, add BaSO 4600-700g adds different in nature graphite 300-350g, adds 200-300g800-1200 purpose Al 2O 3Powder adds 800-1000 purpose ZrO 2Powder 100g adds humic acid 500-600g, and transferring to the lead plaster apparent gravity with pure water is 4.15-4.25g/cm 3
Battery case adopts the ABS engineering material, adopts nylon;
Electrolyte prescription is the phosphoric acid that adds 1% percent by volume in the sulfuric acid solution of 64-65%, adds 0.08% ortho phosphorous acid disodium, adds 0.02%NaSO 4, the CaSO of adding 0.01% 4
2. according to the bike high energy and fully closed lead-acid storage battery described in the claim 1, it is characterized in that, it is hermetically sealed for battery is realized, adopt the excessive design of negative pole, for prevent that pole plate is out of shape, expands in the work of discharging and recharging, in battery case, add an anti-expansion set, the positive and negative electrode group is packed into prevent reinstalling battery case in the expansion set;
The positive grid alloy material of this battery is:
Pb+Ax+By+Cz+Du+Ev+Fw+Gt+Ha
Wherein: A=Sr, K x=0.01～0.6%;
B＝Na 2S 5 y＝0.01～0.6％；
C＝Bi z＝0.001～0.01％；
D＝Cu u＝0.01～0.1％；
E＝Al v＝0.001～0.2％；
F＝Sn w＝0.001～0.8％；
G＝Ag t＝0.001～0.4％；
H＝Te a＝0.001～0.2％
The negative plate grid alloy material of this battery is:
Pb+Ax+Cz+Du+Ev+Fw
Wherein: A=Ca, K, Sr x=0.001～0.4%;
C＝Sn z＝0.01～0.6％；
D＝Bi u＝0.001～0.3％；
E＝Zn v＝0.001～0.2％；
F＝S w＝0.001～0.1％。
3. according to the described a kind of bike high energy and fully closed lead-acid storage battery of claim 1, it is characterized in that,
The positive grid alloy material of this battery is:
Pb+Ax+By+Cz+Du+Ev+Fw+Gt+Ha
Wherein: A=Ca, k x=0.05～0.9%;
B＝Na 2S 4 y＝0.05～0.8％；
C＝Bi z＝0.01～0.03％；
D＝Ce u＝0.07～0.1％；
E＝Al v＝0.06～0.2％；
F＝Zn w＝0.05～0.8％；
G＝Ag t＝0.05～0.3％；
H＝Se a＝0.05～0.2％
The negative plate grid alloy material of this battery is:
Pb+Ax+Cz+Du+Ev+Fw
Wherein: A=Ca, K, Sr x=0.05～0.4%;
C＝Sn z＝0.06～0.7％；
D＝Ag u＝0.01～0.4％；
E＝Zn v＝0.01～0.2％；
F＝Ce w＝0.01～0.1％。
CN200410039160A 2004-02-18 2004-02-18 High-energy all-sealed lead-acid battery without maintaining for submarine Expired - Fee Related CN1591957B (en)

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CN1591957B true CN1591957B (en) 2010-05-26

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Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1331256C (en) * 2005-03-11 2007-08-08 风帆股份有限公司 High-temperature resistant accumulator positive electrode lead plaster and method for preparing same
CN100365861C (en) * 2005-03-11 2008-01-30 北京天睿力迈科技有限公司 High-energy sealed maintenance-free lead-acid accumulator for submarine
CN100403593C (en) * 2005-05-13 2008-07-16 陈有孝 6-HK(M)-55 type high-energy dry-charged sealed maintenance-free lead-acid battery
CN100377412C (en) * 2005-05-13 2008-03-26 陈有孝 12-TK(M)-220 type high-energy dry-charged sealed maintance-free lead-acid battery for tank
CN100359743C (en) * 2005-05-13 2008-01-02 陈有孝 6-TK(M)-360 type high-energy dry-charged sealed maintenance-free lead-acid battery for tank

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1076058A (en) * 1992-02-29 1993-09-08 山东省文登市密闭蓄电池厂 Positive-negative electrode plate grid allog material for sealed lead-acid battery
CN1152803A (en) * 1995-12-22 1997-06-25 陈有孝 Large fully-closed maintenance-free lead-acid accumulator for low-temp. starting

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1076058A (en) * 1992-02-29 1993-09-08 山东省文登市密闭蓄电池厂 Positive-negative electrode plate grid allog material for sealed lead-acid battery
CN1152803A (en) * 1995-12-22 1997-06-25 陈有孝 Large fully-closed maintenance-free lead-acid accumulator for low-temp. starting

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Assignee: Tianjin Ruizhi Control Technology Co., Ltd.

Assignor: Chen Youxiao

Contract record no.: 2010120000137

Denomination of invention: High-energy all-sealed lead-acid battery without maintaining for submarine

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