WO2002101868A1 - A storage battery resistant to pressure and beneficial to environmental protection, which is suitable for being used in deep sea - Google Patents

A storage battery resistant to pressure and beneficial to environmental protection, which is suitable for being used in deep sea Download PDF

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Publication number
WO2002101868A1
WO2002101868A1 PCT/CN2001/001224 CN0101224W WO02101868A1 WO 2002101868 A1 WO2002101868 A1 WO 2002101868A1 CN 0101224 W CN0101224 W CN 0101224W WO 02101868 A1 WO02101868 A1 WO 02101868A1
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WO
WIPO (PCT)
Prior art keywords
battery
pressure
storage battery
grid
resistant
Prior art date
Application number
PCT/CN2001/001224
Other languages
French (fr)
Chinese (zh)
Inventor
Yuesheng Feng
Dian Han
Yifeng Feng
Original Assignee
Yuesheng Feng
Dian Han
Yifeng Feng
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Filing date
Publication date
Application filed by Yuesheng Feng, Dian Han, Yifeng Feng filed Critical Yuesheng Feng
Publication of WO2002101868A1 publication Critical patent/WO2002101868A1/en

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/044—Activating, forming or electrochemical attack of the supporting material
    • H01M4/0445—Forming after manufacture of the electrode, e.g. first charge, cycling
    • H01M4/0447—Forming after manufacture of the electrode, e.g. first charge, cycling of complete cells or cells stacks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/112—Monobloc comprising multiple compartments
    • H01M50/114—Monobloc comprising multiple compartments specially adapted for lead-acid cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • H01M10/12—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • H01M10/12—Construction or manufacture
    • H01M10/16—Suspending or supporting electrodes or groups of electrodes in the case
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0005—Acid electrolytes
    • H01M2300/0011—Sulfuric acid-based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/72—Grids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/30—Arrangements for facilitating escape of gases
    • 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

Definitions

  • the invention relates to a storage battery, in particular to a pressure-resistant and environmentally-friendly storage battery used in deep sea operations.
  • the main components of a commonly used battery include a positive electrode plate group, a negative electrode plate group, an electrolyte, a separator, and an electric tank (container).
  • the positive and negative plates of lead batteries are made of pure lead and the active material is directly formed on it, or the lead frame is made of lead-antimony alloy.
  • the positive electrode (anode) is coated with lead dioxide (Pb0 2 ).
  • the negative electrode (cathode) is coated with an effective substance which is sponge-like pure lead (Pb). The difference between the positive and negative plates of the charge and discharge is used to distinguish the positive and negative electrodes, and the degree of charge and discharge.
  • pole plate group In the same battery, if the number of pole plates of the same polarity exceeds two, they are connected by a battery connection bar, which is called a "pole plate group.
  • Large-capacity battery plates have many plates and small capacity plates. The number is small (the plates mentioned here refer to plates with the same size and material, otherwise they may not meet the above relationship.)
  • each positive plate When assembling the plates, each positive plate must be sandwiched between two negative plates. Both sides of the positive plate can undergo chemical changes, and the same expansion and contraction occur, reducing the chance of bending the positive plate. However, during the charge and discharge cycle of the negative plate, the degree of expansion and contraction is small. If only one side has a chemical change, its effect It is not large.
  • the outermost layer of the electrode plate combination is a negative electrode plate, so the number of negative electrode plates in lead batteries is always one more than that of the positive electrode plate.
  • the thickness of the outermost negative electrode plate is greater than that of the negative electrode sandwiched between the positive electrode plates.
  • the plate is much thinner, typically about half the thickness of the middle negative plate.
  • separator In ordinary lead-acid batteries, apart from a wide gap between a few special combinations of electrode plates, a separator must be inserted between the two electrode plates to prevent the positive and negative electrode plates from contacting each other and causing a short circuit.
  • separators such as wood, hard rubber, and glass, which can be appropriately selected according to the battery program.
  • the container is the battery tank, usually made of glass containers, lead-lined wooden tanks, hard rubber tanks and plastic tanks.
  • Mobile batteries are usually hard rubber or plastic battery tanks.
  • the ordinary lead storage battery described above can only work when the external ambient pressure is 1 atmosphere due to its structure and casing material. When the external ambient pressure exceeds 1 atmosphere, the internal and external pressure imbalance causes the battery to explode. Regardless of whether it is laying cables on the sea floor or moving operations, or the development of deep-sea resources, energy is required. Usually, batteries are used in deep-sea operations and often cannot bear the excessive pressure of the external environment. Therefore, providing energy for deep-sea operations remains to be solved. problem. In addition, a large amount of 30 4 electrolyte is used in ordinary lead storage batteries. Because of the outer casing structure of ordinary lead storage batteries, H 2 S 0 4 escapes or Lead batteries are discarded on the sea floor after use and bring environmental pollution. Ordinary lead batteries are not suitable for deep sea operations. Disclosure of invention
  • the purpose of the present invention is to overcome the existing ordinary storage batteries that cannot exceed 1 atmosphere in the deep sea.
  • the fatal defect of the battery explosion caused by the imbalance of internal and external pressure occurs, and the electrolyte of ordinary lead storage batteries is mainly sulfuric acid, the use of the battery in the deep sea will cause Defects of deep-sea environment pollution, so as to provide a battery that has good performance and can be subjected to excessive external pressure in deep-sea operations.
  • the battery itself has a self-adjusting internal and external pressure balance function. It is convenient to make suitable for deep-sea operations. Used withstand voltage environmental protection type battery.
  • a pressure-resistant and environmentally friendly storage battery suitable for use in deep sea operations provided by the present invention includes: a battery case, a positive and negative grid group, a cotton barrier, a bus plate, a connecting post, and a dielectric.
  • the chemical solution also includes an exhaust hole in the valve-controlled liquid-filling port of the upper cover plate, and a battery self-regulating structure is installed on each valve-controlled liquid-filling port, wherein the battery case is made of ABS engineering plastics and acid-resistant soft plastics are compounded with 8: 2 parts by weight and made into a wall thickness of 3 ⁇ 4.5 mm by conventional methods, which are divided into box-type battery cases with upper cover and lower base;
  • the partition wall is divided into grids, and the general grid number is 2 volts per grid.
  • the grid is made of lead or lead alloy with a regular hexagonal honeycomb mesh grid.
  • the size of the grid is preferably inserted into the lower base of the casing of the box battery.
  • the frame of the negative grid is larger than the honeycomb in the frame. Part is thicker 0. 2 ⁇ 0. 6, the frame of the positive grid is thicker than the honeycomb part in the frame by 0.3 ⁇ 0.8, and the positive and negative grids are coated with lead paste;
  • the negative and positive grids are installed in each grid in the base of the battery casing with no gap between adjacent grids.
  • the positive and negative grids in the same grid are connected in parallel by plate ears. Together, the positive and negative grids between the grid and the grid are connected in series by connecting posts, and then connected to the positive and negative poles; the lower base of the battery is covered with an upper cover installed with a self-regulating structure of the battery, and then a ring is used.
  • Oxygen resin is sealed and fixed; each cell in the battery case is filled with a liquid low-sodium silicon salt prepared by a magnetization process, which is both a dielectric and a chemical conversion liquid.
  • the filled liquid low-sodium silicon salt is filled to fill the battery self-regulating structure.
  • the pressure buffer balance tube in the middle; and the rest except the plate ears on the grid are soaked in the formation solution, soaked for 12 to 24 hours; the formation is conducted by using a formation charger, the formation temperature is: room temperature; the formation time: 30 -50 hours.
  • the battery self-regulating structure It is installed on the valve-controlled liquid-supplying port on the top surface of the upper cover of the battery case.
  • each valve-controlled liquid-supplying port There is a vent hole on the protruding edge of the valve-controlled filling port on the top surface of the upper cover.
  • the filling port covers a hollow pressure-proof seat, which is similar to a bicycle valve and is sealed and fixed.
  • the hollow pressure-proof seat can be made of the same material as the battery case or made of engineering plastic.
  • the hollow pressure-proof seat is sealed and fixed with an elastic material and a pressure buffer balance tube. The length of the tube is affected by the length of the tube.
  • the general design principle is that a pipe with a depth of one meter is 10 cm long and the end of the pipe is closed;
  • the other end of the balance tube is sealed with a plug made of the same material, sealed with glue or sealed with a physical method;
  • the elastic materials used in the pressure buffer balance tube include rubber tubes, latex tubes, rubber tubes for washing machines, and gas Made of rubber hose and other elastic materials;
  • Each cell in the assembled battery case is filled with liquid low-sodium silicon salt, which is both a dielectric and a chemical conversion liquid.
  • the battery needs to be filled with the liquid low-sodium silicon salt to fill the pressure buffer balance tube.
  • the chemical solution is added to the battery tank, the battery tank must be shaken at a constant speed so as to remove air bubbles and fill the entire space with the chemical solution; and all the parts except the ears on the electrode plate are soaked in the chemical solution and soaked for 12 ⁇ 24 hours, so that the chemical solution penetrates the electrode plate and the cotton, so that it does not generate heat during the chemical conversion, and achieves complete chemical conversion;
  • the liquid low-sodium silicon salt filled in the battery tank described therein is made by a magnetization process:
  • the inorganic acid includes: hydrochloric acid, oxalic acid, and sulfuric acid; a pH value of 4-5 is preferred;
  • the stirring includes manual stirring or mechanical stirring, the mechanical stirring speed is 700 ⁇ 1400 rpm, and stirring for 5 ⁇ 10 minutes, so that the mixture obtained in step 4 is Reduce the viscosity, measure the viscosity with a rotary viscometer while stirring, and stop stirring when the viscosity is less than 0.02 poise (mPas) to obtain a liquid low sodium silicon salt for a battery;
  • the water according to the present invention includes: distilled water and deionized water.
  • the advantages of the present invention are: 1.
  • the present invention solves the problem that general lead-acid batteries cannot be used in the deep sea;
  • the battery case of the present invention is thicker than ordinary battery walls, but can withstand a certain external pressure than the existing ones
  • the battery has a thin wall, and the battery is filled with a liquid low-sodium silicon salt (both an electrolyte and a chemical liquid) made by the magnetization process of the present invention, and combined with a self-regulating structure installed on the battery cover.
  • the battery which can work below 6000 meters in the deep sea, provides a new environmentally friendly energy source for the deep sea exploration, defense, and communications industries.
  • the present invention overcomes a large number of lead-acid batteries have been used 304 causing environmental pollution and seriously endanger the process of manufacturing the battery caused workers, while also avoiding the usual lead-acid batteries using a large number of sulfuric acid storage battery caused S0 4 Corrosion of the interface, and the problem of acid leakage in the transportation of the battery, so the economic and social benefits are significant.
  • the battery of the present invention has the following properties:
  • the battery standard of the produced deep-sea battery is 100; the specific energy is greatly improved, reaching more than 53W / kg; the service life is increased to more than 400 times; the deep-sea battery has high cold resistance It can be used normally at a temperature of -50 ° C ⁇ + 60 ° C; the starting capacity is improved from the general 3-7C discharge capacity to a discharge capacity above 30C; the battery has a small self-discharge electrode and a long-term storage period of 18 Can be used normally for months.
  • BRIEF DESCRIPTION OF THE DRAWINGS BRIEF DESCRIPTION OF THE DRAWINGS
  • Figure 1 is a schematic diagram of the main structure of a deep-sea battery of the present invention
  • FIG. 2 is a schematic structural diagram of a hollow pressure-proof seat of a deep-sea battery according to the present invention
  • FIG. 3 is a schematic structural diagram of a pressure buffer balance tube installed on a deep-sea battery of the present invention.
  • FIG. 4 is a constant current discharge diagram of the 12V100Ah 3C (300A), 2C (200A :), and 1C (100A) batteries of the present invention.
  • liquid low sodium silicon salt is prepared as both an electrolyte and a chemical liquid:
  • step 4 Stir the magnetized mixture in step 4 with a stirrer at a stirring speed of 700 to 1400 rpm and stir for 5 to 10 minutes to reduce the viscosity of the mixture obtained in step 4.
  • a rotational viscometer while stirring. Measure the viscosity, stop stirring when the viscosity is less than 0.02 poise (mPas), and obtain a liquid low sodium silicon salt for a battery;
  • a 12V100Ah battery capable of operating at a depth of 6000 meters in the deep sea is made.
  • ABS engineering plastic and polystyrene are prepared at 8: 2 (weight ratio) to prevent material from bursting under pressure.
  • the method is to make a casing of a box-type battery with a wall thickness of 3 mm ⁇ length 150 mm ⁇ width 95 legs.
  • the casing is divided into a base 1 and an upper cover plate 11.
  • the casing base 1 is evenly divided into 6 cells by partition walls 12 and the bottom surface of the cell.
  • the height of the saddles 5 is 50% higher than that of ordinary saddles. The purpose is to help the air bubbles in the battery case to be driven away.
  • the upper cover plate 11 is rectangular and closely matches the housing base 1. On the top surface of the battery upper cover plate 11, there are 6 ⁇ 10 ⁇ normally valve-controlled filling ports 9, and the position of each filling port 9 corresponds to the center position of each cell in the housing base 1. There are two ⁇ 1 bandit exhaust holes 14 on the protruding edge of the port 9, and a hollow pressure-proof seat 15 as shown in FIG. 2 is placed on each liquid-filling port 9, and is sealed and sealed with sealing glue. Seat 15 is made of elastic rubber material, or plastic material, plastic material.
  • Each hollow pressure-proof seat 15 is covered with a ⁇ outer diameter im X length 600mm X wall thickness 3
  • the outer surface of the buffer balance tube 16 is sealed with epoxy resin, and the end of the tube is made of a sealing plug 17 made of the same material. Closed.
  • a grid and a spacer made of ordinary materials are fixedly arranged in each grid.
  • a negative grid 2 with a positive hexagonal honeycomb network is placed from the first grid, and the positive grid 3 is interposed.
  • the negative and positive grids 2 and 3 A 1.2mm-thick spacer 4 is placed in between, and the main structure of the installed battery is shown in FIG. 1.
  • the thickness of the negative grid 2 is 0.8 bandit, the thickness of the frame is 1.2, and the thickness of the positive grid 3 is 1.2 mm, and the thickness of the frame is L 8mm.
  • the oxygen resin is sealed well, and no ventilation is allowed between each cell.
  • the liquid low-sodium silicon salt prepared in Example 1 is injected into each cell in the tank. It is both a dielectric and a chemical conversion liquid.
  • the salt fullness is filled with the pressure buffer balance tube.
  • a formation charger to perform energization. For example, use "uc-KGCFD2 economical 40-circuit charge and discharge power supply” to energize the battery installed in step 4.
  • the formation temperature is: room temperature; the formation time: 30-50 hours, 48 hours is the best Formation voltage is 2.2V.
  • the battery produced in this embodiment is equipped with a battery self-regulating structure.
  • the battery self-regulating structure is provided with two vent holes on the edge of each valve-controlled filling port on the battery cover, and the valve-controlled filling port jacket is hollow to prevent pressure.
  • a self-regulating structure for a battery composed of a seat and a hollow pressure-proof seat that communicates with each exhaust hole.
  • One end of the sealed pressure-buffering balance tube is covered by the outside of the hollow pressure-proof seat. It is in communication with the internal cavity of the battery.
  • the pressure buffer balance tube can be flattened a little, and the liquid is pushed into the battery case to improve the pressure resistance in the case.
  • An environmentally friendly battery that maintains internal and external pressure balance and has self-regulating pressure.
  • the battery produced in this embodiment used in the deep sea has good performance: (1) No bubbles are generated during discharge;
  • the battery case filled with liquid low-sodium silicon salt dielectric is made by a magnetization process, which is both a dielectric and a chemical fluid, which greatly reduces the number of processes in the battery manufacturing process and reduces the labor intensity of workers;
  • the filling dielectric needs to be filled to fill the pressure buffer balance tube.
  • the specific gravity is 1. 32. Therefore, the current and voltage of the battery remain stable under a large external pressure;
  • the battery can be used normally at a temperature of -50 ° C to + 60 ° C, and the deep-sea battery of the present invention can work normally when the temperature changes greatly in the deep sea, and the discharge point voltage is stable;
  • a 12V200Ah deep-sea battery is produced.
  • the main structure of the deep-sea battery is the same as that of Examples 1 and 2. The difference is that four ⁇ lmm exhaust holes 14 are opened on the protruding edge of a valve-controlled filling port 9 to add liquid.
  • a hollow pressure-proof seat 15 as shown in FIG. 2 is put on the mouth 9 so that the hollow pressure-proof seat 15 communicates with four ⁇ lmm exhaust holes 14 and is sealed and fixed with sealing glue 7.
  • a hollow pressure-proof seat 15 is sheathed.
  • a deep-sea battery with a 10-hour rate of 12V38Ah and operating at 6000 meters was produced.
  • the size of the battery was 197 mm in length X 65 mm in width X 172 mm in height.
  • the main structure of the deep-sea battery, the electrolyte, and the formation solution were the same as those in Examples 1 and 1. 2 is the same, the difference is that two 4> lmm exhaust holes 14 are opened on the protruding edge of each valve-controlled filling port 9, and the end of the tube is closed with a sealant.
  • the prepared deep-sea storage battery has no acid mist discharge and good recovery performance; the capacity is greater than 40Ah.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to a storage battery resistant to pressure and beneficial to environmental protection, which is suitable for being used in deep sea. The storage battery uses a case, the wall of which is thicker than that of an ordinary case, but thinner than that of a storage battery case having resistance to pressure to some extent. The storage battery contains a liquid low-sodium silicate electrolyte, which is both a electrolyte and a forming solution, and manufactured by magnetization process. A self adjustable-pressure part is mounted on the top of the upper lid plate of the battery. The storage battery is able to operate at the depth of 6000 meters below sea level. A storage battery has a specific energy of 53W/kg or more and the service life of the storage battery increases to 400 times or more. The storage battery has resistance to low and high temperature and operates normally at the temperature of -50°C∩+60°C. The start power increases from 3-7C discharge capacity to 30C discharge capacity. The battery has extremely low self-discharge and can operate normally after being stored for 18 months. There is provided a new power source for exploring in sea, national defense and communication.

Description

适于深海作业中使用的耐压环保蓄电池 技术领域  Voltage-resistant environmentally friendly storage battery suitable for use in deep sea operations
本发明涉及一种蓄电池， 特别是涉及一种在深海作业中使用的耐压环保蓄 电池。  The invention relates to a storage battery, in particular to a pressure-resistant and environmentally-friendly storage battery used in deep sea operations.
背景技术 Background technique
通常使用的蓄电池主要构成部分有正极板组、 负极板组、 电解液、 隔离物 和电槽（容器） 等。 铅蓄电池的正、 负极板是由纯铅制成基板， 有效物质直接 在上面形成， 或者用铅锑合金制成栅架， 正极 （阳极）上涂以有效物质是二氧 化铅（Pb02)， 负极（阴极）上涂以有效物质是海绵状纯铅 (Pb)。 通过充放电正、 负极板颜色变的不同， 以此区别出正极和负极， 和充放电的程度。 The main components of a commonly used battery include a positive electrode plate group, a negative electrode plate group, an electrolyte, a separator, and an electric tank (container). The positive and negative plates of lead batteries are made of pure lead and the active material is directly formed on it, or the lead frame is made of lead-antimony alloy. The positive electrode (anode) is coated with lead dioxide (Pb0 2 ). The negative electrode (cathode) is coated with an effective substance which is sponge-like pure lead (Pb). The difference between the positive and negative plates of the charge and discharge is used to distinguish the positive and negative electrodes, and the degree of charge and discharge.
. 在同一个电池内， 其同极性的极板片数超过两片者， 用电池连接条联接起 来称为 "极板组， 大容量的蓄电池极板片数多， 容量小的极板片数少 （在这里 所说的极板是指尺寸和材料完全相同的极板， 否则不一定符合上述关系）。 在装 配极板时， 必须使每一片正极板夹在二片负极板之间， 使得正极板的两面都能 起化学变化， 发生同样的膨胀和收缩， 减少正极板弯曲的机会。 而负极板在充 放电循环中， 膨胀、 收缩程度较小， 如果仅一面起化学变化， 其影响也不大。 所以在极板组合的最外层都是负极板， 因此在铅蓄电池中负极板片数总比正极 板多一片。 最外层的负极板厚度， 较夹在正极板中间的负极板薄得多， 一般约 为中间负极板厚度的一半。 In the same battery, if the number of pole plates of the same polarity exceeds two, they are connected by a battery connection bar, which is called a "pole plate group. Large-capacity battery plates have many plates and small capacity plates. The number is small (the plates mentioned here refer to plates with the same size and material, otherwise they may not meet the above relationship.) When assembling the plates, each positive plate must be sandwiched between two negative plates. Both sides of the positive plate can undergo chemical changes, and the same expansion and contraction occur, reducing the chance of bending the positive plate. However, during the charge and discharge cycle of the negative plate, the degree of expansion and contraction is small. If only one side has a chemical change, its effect It is not large. Therefore, the outermost layer of the electrode plate combination is a negative electrode plate, so the number of negative electrode plates in lead batteries is always one more than that of the positive electrode plate. The thickness of the outermost negative electrode plate is greater than that of the negative electrode sandwiched between the positive electrode plates. The plate is much thinner, typically about half the thickness of the middle negative plate.
在通常的铅蓄电池中， 除少数特殊组合的极板间留有宽大的空隙外， 在两 极板间均需***隔离物， 以防止正负极板相互接触而发生短路。 隔离物有木质、 硬橡胶、 玻璃等数种， 可根据蓄电池的程式适当选定。  In ordinary lead-acid batteries, apart from a wide gap between a few special combinations of electrode plates, a separator must be inserted between the two electrode plates to prevent the positive and negative electrode plates from contacting each other and causing a short circuit. There are several types of separators, such as wood, hard rubber, and glass, which can be appropriately selected according to the battery program.
. 容器即蓄电池的电槽， 通常有玻璃容器、 衬铅木槽、 硬橡胶电槽和塑料电 槽制成的。 移动式蓄电池则常用硬橡胶或塑料电池槽。 The container is the battery tank, usually made of glass containers, lead-lined wooden tanks, hard rubber tanks and plastic tanks. Mobile batteries are usually hard rubber or plastic battery tanks.
所述的通常的铅蓄电池由于它的构造和外壳材料所决定， 只能在外部环境 压力为 1个大气压时工作， 当外部的环境压力超过 1个大气压时， 内外压不平 衡造成电池***。 而无论是海底铺设电缆还是进行移动作业， 还是深海资源的 开发都需要能源， 通常蓄电池用于深海作业又往往遇到承受不了外部环境过大 压力， 因此， 为深海作业提供能源是呈待解决的问题。 另外， 普通的铅蓄电池 中大量使用 304电解质， 由于普通的铅蓄电池外箱结构常常造成 H2S04逸出或 铅蓄电池使用完废弃在海底而带来环境污染， 普通的铅蓄电池不适宜用在深海 作业。 发明的公开 The ordinary lead storage battery described above can only work when the external ambient pressure is 1 atmosphere due to its structure and casing material. When the external ambient pressure exceeds 1 atmosphere, the internal and external pressure imbalance causes the battery to explode. Regardless of whether it is laying cables on the sea floor or moving operations, or the development of deep-sea resources, energy is required. Usually, batteries are used in deep-sea operations and often cannot bear the excessive pressure of the external environment. Therefore, providing energy for deep-sea operations remains to be solved. problem. In addition, a large amount of 30 4 electrolyte is used in ordinary lead storage batteries. Because of the outer casing structure of ordinary lead storage batteries, H 2 S 0 4 escapes or Lead batteries are discarded on the sea floor after use and bring environmental pollution. Ordinary lead batteries are not suitable for deep sea operations. Disclosure of invention
本发明的目的在于克服已有普通蓄电池在深海下使用不能超过 1 个大气 压， 一旦出现内外压不平衡引起电池***的致命缺陷， 以及普通的铅蓄电池的 电解质主要是硫酸成分， 在深海下使用造成对深海环境污染的缺陷， 从而提供 一种性能良好的、 能在深海作业中受到外压过大时， 蓄电池本身具有自调节内、 外压平衡一致功能的、 制做方便的适于深海作业中使用的耐压环保型蓄电池。  The purpose of the present invention is to overcome the existing ordinary storage batteries that cannot exceed 1 atmosphere in the deep sea. Once the fatal defect of the battery explosion caused by the imbalance of internal and external pressure occurs, and the electrolyte of ordinary lead storage batteries is mainly sulfuric acid, the use of the battery in the deep sea will cause Defects of deep-sea environment pollution, so as to provide a battery that has good performance and can be subjected to excessive external pressure in deep-sea operations. The battery itself has a self-adjusting internal and external pressure balance function. It is convenient to make suitable for deep-sea operations. Used withstand voltage environmental protection type battery.
本发明的目的是这样实现的： 本发明提供的一种适于深海作业中使用的耐 压环保蓄电池， 包括： 电池壳体、 正、 负板栅组、 隔棉、 汇流板、 连接柱、 电 介质、 化成液， 还包括在上盖板的阀控加液口上开有排气孔， 并在每一阀控加 液口上安装电池自调压结构组成， 其中所述的电池壳体是由釆用 ABS工程塑料 与耐酸的软塑料以 8 : 2重量份配料， 经常规方法制成壁厚 3〜4. 5mm的， 分为 上盖板、 下底座的箱式电池壳体； 下底座内设置的隔墙分为格， 一般格数为 2 伏一格； 格内底面上有凸起筋状的鞍子， 极板安放在鞍子上， 鞍子的高度比一 般蓄电池内的鞍子高 50%，；  The purpose of the present invention is achieved as follows: A pressure-resistant and environmentally friendly storage battery suitable for use in deep sea operations provided by the present invention includes: a battery case, a positive and negative grid group, a cotton barrier, a bus plate, a connecting post, and a dielectric. The chemical solution also includes an exhaust hole in the valve-controlled liquid-filling port of the upper cover plate, and a battery self-regulating structure is installed on each valve-controlled liquid-filling port, wherein the battery case is made of ABS engineering plastics and acid-resistant soft plastics are compounded with 8: 2 parts by weight and made into a wall thickness of 3 ~ 4.5 mm by conventional methods, which are divided into box-type battery cases with upper cover and lower base; The partition wall is divided into grids, and the general grid number is 2 volts per grid. There are raised saddles on the bottom surface of the grid. The plates are placed on the saddles. The height of the saddles is 50% higher than the saddles in ordinary batteries.
所述的板栅是用铅或铅合金制成正六角形蜂窝网状的板栅， 大小以刚好装 入箱式电池的壳体下底座内为宜，负板栅的边框比边框内的蜂网部分要厚 0. 2〜 0. 6, 正板栅的边框比边框内的蜂网部分要厚 0. 3〜0. 8， 并且正、 负板栅上涂 有铅膏；  The grid is made of lead or lead alloy with a regular hexagonal honeycomb mesh grid. The size of the grid is preferably inserted into the lower base of the casing of the box battery. The frame of the negative grid is larger than the honeycomb in the frame. Part is thicker 0. 2 ~ 0. 6, the frame of the positive grid is thicker than the honeycomb part in the frame by 0.3 ~ 0.8, and the positive and negative grids are coated with lead paste;
其中负、 正板栅与隔棉相间安装在电池壳体底座内的每一格内， 相邻板栅之 间不留空隙， 同一格内的正、 负板栅用汇流板各自通过板耳并联起来， 格与格 之间的正、 负板栅分别通过连接柱串联连接， 再连接到正、 负极柱上； 电池下 底座上盖好安装有电池自调压结构的上盖板， 再用环氧树脂密封固定； 电池壳 内每一格灌满既是电介质又作为化成液的采用磁化工艺制得的液态低钠硅盐， 所灌装液态低钠硅盐的充满度以充满电池自调压结构中的压力缓冲平衡管为 止； 并除板栅上的板耳外其余部分全部泡在化成液中， 浸泡 12〜24小时； 用化 成充电机进行通电化成， 化成温度为： 室温； 化成时间： 30-50小时。  The negative and positive grids are installed in each grid in the base of the battery casing with no gap between adjacent grids. The positive and negative grids in the same grid are connected in parallel by plate ears. Together, the positive and negative grids between the grid and the grid are connected in series by connecting posts, and then connected to the positive and negative poles; the lower base of the battery is covered with an upper cover installed with a self-regulating structure of the battery, and then a ring is used. Oxygen resin is sealed and fixed; each cell in the battery case is filled with a liquid low-sodium silicon salt prepared by a magnetization process, which is both a dielectric and a chemical conversion liquid. The filled liquid low-sodium silicon salt is filled to fill the battery self-regulating structure. And the pressure buffer balance tube in the middle; and the rest except the plate ears on the grid are soaked in the formation solution, soaked for 12 to 24 hours; the formation is conducted by using a formation charger, the formation temperature is: room temperature; the formation time: 30 -50 hours.
其中本发明正极板膏：由铅粉 100公斤、石墨 500克、短纤纸 50克、硫酸 12. 26 公斤（是 25°C d=1. 38)、 水 14公斤混合而成， 铅膏密度为 2 克 /cm3； 本发明负极板所涂铅膏： 由铅粉 100公斤、硫酸钡 500克、 短纤纸 50克、 硫酸 8. 19公斤（是 25°C d=l. 38)、水 14公斤混合而成，铅膏密度为 4. 3克 /cm3； 所述的电池自调压结构是安装在通常电池壳上盖板的顶面上的阀控加液口 上， 可以在每个阀控加液口上安装一个， 也可以任意选择安装 1-6个； 所述的 电池自调压结构是在上盖板顶面上的阀控加液口凸出的边缘上开有排气孔， 加 液口外套一个中空防压座， 该中空防压座类似自行车的气门， 并密封固定住， 中空防压座可以用与电池壳相同的材料或由具有工程塑料制做的， 中空防压座 外密封包覆固定一根弹性材料制做的压力缓冲平衡管， 该管的长短按使用时受 压大小计算， 一般设计原则以水深一米管长 10公分， 该管的末端封闭； 例如压 力缓冲平衡管的另一端用同种材料作的塞子密封住、 用胶密封住或采用物理办 法密封住； 其中压力缓冲平衡管所用的弹性材料包括橡胶管、 乳胶管、 洗衣机 用的胶管、 煤气用的胶管和其他具有弹性材料制做的； 26 of the present invention positive electrode paste: 100 kg of lead powder, 500 grams of graphite, 50 grams of short fiber paper, 12.26 sulfuric acid Kg (25 ° C d = 1.38) and 14 kg of water, the density of lead paste is 2 g / cm 3 ; the lead paste coated on the negative electrode plate of the present invention: 100 kg of lead powder, 500 g of barium sulfate, 50 g of staple fiber paper, 8.19 kg of sulfuric acid (25 ° C d = 1.38), 14 kg of water, lead paste density of 4.3 g / cm 3 ; the battery self-regulating structure It is installed on the valve-controlled liquid-supplying port on the top surface of the upper cover of the battery case. One can be installed on each valve-controlled liquid-supplying port, or you can choose to install 1-6. There is a vent hole on the protruding edge of the valve-controlled filling port on the top surface of the upper cover. The filling port covers a hollow pressure-proof seat, which is similar to a bicycle valve and is sealed and fixed. The hollow pressure-proof seat can be made of the same material as the battery case or made of engineering plastic. The hollow pressure-proof seat is sealed and fixed with an elastic material and a pressure buffer balance tube. The length of the tube is affected by the length of the tube. For calculation of pressure, the general design principle is that a pipe with a depth of one meter is 10 cm long and the end of the pipe is closed; The other end of the balance tube is sealed with a plug made of the same material, sealed with glue or sealed with a physical method; the elastic materials used in the pressure buffer balance tube include rubber tubes, latex tubes, rubber tubes for washing machines, and gas Made of rubber hose and other elastic materials;
其中将组装好的电池壳内的每一格中灌满液态低钠硅盐， 它既是电介质又 作为化成液， 电池内所需灌装液态低钠硅盐的充满度以充满压力缓冲平衡管为 止； 其中当往电池槽内加入化成液时， 一定匀速振动电池槽， 以便除掉气泡让 其整个空间充满化成液； 并且除极板上的板耳外其余部分全部泡在化成液中， 浸泡 12〜24小时， 使化成液浸透极板和隔棉， 这样在化成时不发热， 达到化成 彻底；  Each cell in the assembled battery case is filled with liquid low-sodium silicon salt, which is both a dielectric and a chemical conversion liquid. The battery needs to be filled with the liquid low-sodium silicon salt to fill the pressure buffer balance tube. When the chemical solution is added to the battery tank, the battery tank must be shaken at a constant speed so as to remove air bubbles and fill the entire space with the chemical solution; and all the parts except the ears on the electrode plate are soaked in the chemical solution and soaked for 12 ~ 24 hours, so that the chemical solution penetrates the electrode plate and the cotton, so that it does not generate heat during the chemical conversion, and achieves complete chemical conversion;
. 其中所述的电池槽内灌装的液态低钠硅盐是采用磁化工艺制得的：  The liquid low-sodium silicon salt filled in the battery tank described therein is made by a magnetization process:
( 1 ) 取含 40〜60wt°/。 3 2的硅溶胶 5〜15重量份； (1) Take 40 ~ 60wt ° /. 5 2 to 15 parts by weight of silica sol;
(2)边搅拌边加入水到步骤 1的硅溶胶中， 加入 15〜25重量份水， 用波 美比重计***该混合物中测量波美浓度， 当波美浓度为 0. 65〜0. 85% ¾e，时不 再加入水为止； 所述的水是去离子水或蒸馏水；  (2) While stirring, add water to the silica sol of step 1, add 15 ~ 25 parts by weight of water, insert the mixture with a Baume hydrometer to measure the Baume concentration, and when the Baume concentration is 0.65 ~ 0. 85 % ¾e, when no more water is added; the water is deionized water or distilled water;
( 3) 用无机酸调节混合物的 pH值， 取上述步骤 2所得的产物中加入无机 酸混合， 边加入无机酸边测量该混合物的 pH值， 直到 pH值为 1〜4时停止加入 无机酸； 所述的无机酸包括： 盐酸、 草酸、 硫酸； pH值为 4-5为优选；  (3) adjusting the pH of the mixture with an inorganic acid, adding the inorganic acid to the product obtained in the above step 2 and measuring the pH of the mixture while adding the inorganic acid, and stopping adding the inorganic acid until the pH value is 1 to 4; The inorganic acid includes: hydrochloric acid, oxalic acid, and sulfuric acid; a pH value of 4-5 is preferred;
(4) 把上述步骤 3所得的混合物放到一个具有 1000〜6000高斯的磁场进 行磁化 5〜10分钟； 具有 1000~6000高斯磁场是用钕铁硼磁性材料、 铁氧体磁 性材料或其它磁性材料制作的一圆桶， 将其混合物放在圆桶进行磁化， 或者是 一交、 直流磁场。 (4) Put the mixture obtained in the above step 3 into a magnetic field with 1000 ~ 6000 Gauss for magnetization for 5 ~ 10 minutes; with a magnetic field of 1000 ~ 6000 Gauss, use NdFeB magnetic material, ferrite magnetic material or other magnetic materials Make a drum, put the mixture in the drum for magnetization, or One AC, DC magnetic field.
(5 ) 将上述步骤 4磁化后的混合物进行搅泮， 其搅拌包括人工搅拌或机械 搅拌， 其机械搅摔速度为 700〜1400转 /分， 搅拌 5〜10分钟， 使步骤 4所得的 混合物其粘度降低，边搅拌边用旋转粘度计测量粘度，当粘度小于 0. 02泊 (mPas) 时停止搅拌， 制得蓄电池用液态低钠硅盐；  (5) Stirring the magnetized mixture in step 4 above, the stirring includes manual stirring or mechanical stirring, the mechanical stirring speed is 700 ~ 1400 rpm, and stirring for 5 ~ 10 minutes, so that the mixture obtained in step 4 is Reduce the viscosity, measure the viscosity with a rotary viscometer while stirring, and stop stirring when the viscosity is less than 0.02 poise (mPas) to obtain a liquid low sodium silicon salt for a battery;
本发明所述的水包括： 蒸馏水和去离子水。  The water according to the present invention includes: distilled water and deionized water.
本发明的优点在于： 1.本发明解决了一般的铅酸蓄电池不能在深海中使用 的问题； 本发明的蓄电池壳体釆用较通常蓄电池壁厚， 但又比已有的可耐一定 外压的蓄电池壁薄， 蓄电池内灌装的是本发明的磁化工艺制作的液态低钠硅盐 (既是电解质又是化成液)， 并结合安装在蓄电池盖上的自调压的结构做成的一 种可以在深海 6000米以下工作的蓄电池， 为深海勘探、 国防、 通讯业提供一种 新环保型能源。  The advantages of the present invention are: 1. The present invention solves the problem that general lead-acid batteries cannot be used in the deep sea; the battery case of the present invention is thicker than ordinary battery walls, but can withstand a certain external pressure than the existing ones The battery has a thin wall, and the battery is filled with a liquid low-sodium silicon salt (both an electrolyte and a chemical liquid) made by the magnetization process of the present invention, and combined with a self-regulating structure installed on the battery cover. The battery, which can work below 6000 meters in the deep sea, provides a new environmentally friendly energy source for the deep sea exploration, defense, and communications industries.
2. 本发明克服了已有铅酸蓄电池大量使用 304造成环境污染， 以及在制 造电池的过程中对工人带来的严重危害， 另外也避免了通常铅酸蓄电池大量使 用 S04造成硫酸对蓄电池接口的腐蚀， 以及在蓄电池运输中所出现的漏酸的问 题， 因此经济和社会效益显著。 2. The present invention overcomes a large number of lead-acid batteries have been used 304 causing environmental pollution and seriously endanger the process of manufacturing the battery caused workers, while also avoiding the usual lead-acid batteries using a large number of sulfuric acid storage battery caused S0 4 Corrosion of the interface, and the problem of acid leakage in the transportation of the battery, so the economic and social benefits are significant.
3. 本发明的蓄电池具有如下性能： 所制作的深海蓄电池其电池标准为 100; 比能量大大地提高了， 达到 53W/kg以上； 使用寿命提髙到 400次以上； 该深海 蓄电池有耐高寒髙温的能力， 可在- 50°C〜+60°C的温度下正常使用； 起动能力 从一般的 3- 7C放电能力提高到 30C以上放电能力； 该蓄电池自放电极小， 长期 保存期到 18个月都能正常使用。 附图说明  3. The battery of the present invention has the following properties: The battery standard of the produced deep-sea battery is 100; the specific energy is greatly improved, reaching more than 53W / kg; the service life is increased to more than 400 times; the deep-sea battery has high cold resistance It can be used normally at a temperature of -50 ° C ~ + 60 ° C; the starting capacity is improved from the general 3-7C discharge capacity to a discharge capacity above 30C; the battery has a small self-discharge electrode and a long-term storage period of 18 Can be used normally for months. BRIEF DESCRIPTION OF THE DRAWINGS
图 1是本发明的深海蓄电池主体结构示意图  Figure 1 is a schematic diagram of the main structure of a deep-sea battery of the present invention
图 2是本发明的深海蓄电池的中空防压座结构示意图  FIG. 2 is a schematic structural diagram of a hollow pressure-proof seat of a deep-sea battery according to the present invention;
图 3是本发明的深海蓄电池上装有压力缓冲平衡管的结构示意图 图 4是本发明的 12V100Ah 3C (300A)、 2C (200A：)、 1C ( 100A)蓄电池恒 流放电图  FIG. 3 is a schematic structural diagram of a pressure buffer balance tube installed on a deep-sea battery of the present invention. FIG. 4 is a constant current discharge diagram of the 12V100Ah 3C (300A), 2C (200A :), and 1C (100A) batteries of the present invention.
图 4图面说明：  Figure 4 illustrates the figure:
3C放电曲线（本发明的蓄电池） 9. 8分钟电压下降到 10. 5 V 2C放电曲线（本发明的蓄电池） 24. 6分钟电压下降到 10. 5 V 1C放电曲线 （本发明的蓄电池） 48分钟电压下降到 10. 5 V 具体实施方式 3V discharge curve (the battery of the present invention) 9. 8 minutes voltage drops to 10. 5 V 2C discharge curve (the battery of the invention) 24. 6 minutes voltage drops to 10. 5 V 1V Discharge curve (the storage battery of the present invention) The voltage drops to 10. 5 V in 48 minutes
实施例 1  Example 1
首先制取液态低钠硅盐既作电解质又作化成液：  First, the liquid low sodium silicon salt is prepared as both an electrolyte and a chemical liquid:
( 1 ) 取含 60wt°/。SiO2的的硅溶胶 5重量份， 共用 5公斤硅溶胶； (1) Take 60wt ° /. 5 parts by weight of silica sol of SiO 2 , sharing 5 kg of silica sol;
. (2) 边搅拌边加入蒸馏水到步骤 1的硅溶胶中， 加入约 2重量份水， 实际 用水 15升， 用波美比重计***该混合物中测量波美浓度， 当波美浓度为 0. 65% ¾e'时不再加入水为止； (2) Add distilled water to the silica sol of step 1 while stirring, add about 2 parts by weight of water, 15 liters of actual water, insert the mixture with a Baume hydrometer to measure the Baume concentration, and when the Baume concentration is 0. 65% ¾e 'until no more water is added;
(3 ) 向上述步骤（2)所得的混合物中加入硫酸 2升混合， 边加入硫酸边 测量该混合物的 pH值为 4为止；  (3) adding 2 liters of sulfuric acid to the mixture obtained in the above step (2) and mixing, and measuring the pH of the mixture until the pH is 4 while adding sulfuric acid;
(4)把上述步骤 3所得的混合物放到一个用钕铁硼磁性材料制作的直径为 800mmX桶高 600讓圆桶中心， 该圆桶内具有 5000髙斯的磁场进行磁化 8分钟； (4) Put the mixture obtained in the above step 3 into a cylinder made of neodymium-iron-boron magnetic material with a diameter of 800mmX and a height of 600 to make the center of the drum, and the drum has a magnetic field of 5000 髙 s for magnetization for 8 minutes;
(5)将上述步骤 4磁化后的混合物用搅拌机进行搅拌，其搅拌速度为 700〜 1400转 /分， 搅拌 5〜10分钟， 使步骤 4所得的混合物其粘度降低， 边搅拌边 用旋转粘度计测量粘度， 当粘度小于 0. 02泊 (mPas)时停止搅拌， 制得蓄电池用 液态低钠硅盐； (5) Stir the magnetized mixture in step 4 with a stirrer at a stirring speed of 700 to 1400 rpm and stir for 5 to 10 minutes to reduce the viscosity of the mixture obtained in step 4. Use a rotational viscometer while stirring. Measure the viscosity, stop stirring when the viscosity is less than 0.02 poise (mPas), and obtain a liquid low sodium silicon salt for a battery;
实施例 2  Example 2
制做一种 12V100Ah的、 可在深海 6000米下工作的蓄电池， 由 8: 2 (重量 比） 的 ABS工程塑料与聚苯乙烯配制成防止受压***的材料， 用该材料采用通 常的热铸方法制成壁厚 3 mmX长 150mmX宽 95腿的箱式电池的壳体， 壳体分底 座 1和上盖板 11， 壳体底座 1内由隔墙 12均匀分隔成 6个格， 格内底面上有 凸起筋状的鞍子 5， 极板安放在鞍子 5上， 鞍子 5的高度比一般的鞍子高 50%， 目的是利于电池壳内气泡被赶走， 达到化成时不发热使化成充分； 上盖板 11呈 长方形与壳体底座 1密合相配。 电池上盖板 11的顶面上有 6个 Φ ΙΟιηπι的通常 阀控加液口 9， 每个加液口 9的位置对应壳体底座 1 内每个格的中心位置上， 在每个加液口 9凸出的边缘上开有 2个 Φ 1匪排气孔 14， 每个加液口 9上套一 个如图 2所示的中空防压座 15， 并用封口胶密封固定住， 中空防压座 15 由具 有弹性的橡胶材料、 或塑料材料、 塑胶材料制做的， 每个中空防压座 15外套一 根 Φ外径 im X长度 600mmX壁厚 3 讓带有加强筋的橡胶管做为压力缓冲平 衡管 16， 其接口的外面用环氧树脂密封， 该管的末端用同样材料做的密封塞 17 封闭。 在每格内固定安放板栅与通常材料制作的隔棉， 从第一格贴壁放一具有 正六角形蜂窝网的负极板栅 2， 正极板栅 3相间安放， 负、 正极栅 2、 3之间安 置一 1. 2mm厚的隔棉 4， 安装好的电池主体结构如图 1所示。 其中负板栅 2厚 度为 0. 8匪， 边框厚度为 1. 2瞧， 正极板栅 3厚度为 1. 2mm, 边框厚度为 L 8mm。 正极栅 3涂以由铅粉 100公斤、石墨 500克、短纤纸 50克、硫酸 12. 26公斤（是 25°C d=1. 38)、 水 14公斤混合而成的铅膏， 铅膏密度为 4. 2 克 /cm3 ； 负极栅 涂以由铅粉 100公斤、 硫酸钡 500克、 短纤纸 50克、 硫酸 8. 19公斤 （是 25°C d-1. 38), 水 14公斤混合而成的铅膏， 铅膏密度为 4. 3 克 /cm3 。 负、 正极栅 2 与隔棉 3之间没有空隙， 依次类推， 每一格内共有 6片负板栅 2， 5片正板栅 3 和 10片隔棉 4; 用一铅汇流板 6把每一格内的正、 负板栅各自并联起来， 格与 格之间的正、 负板栅分别通过连接柱 10 (图中未示出） 串联连接， 再分别连接 到正、 负极柱 7、 8上， 板栅、 极柱和连接柱之间的连接方式同通常蓄电池安装 方式一样， 然后将安装好的电池的下底座上盖好已安有电池自调压结构的电池 盖板 11， 用环氧树脂密封好， 每一个格之间不能有通气； 把实施例 1 已配制 好的液态低钠硅盐注入槽中每一格， 它既是电介质又作为化成液， 所灌装的液 态低钠硅盐充满度以充满压力缓冲平衡管内为止； 在往电池槽内加入化成液时， 在将蓄电池放在匀速振动的振动机上匀速振动电池槽， 除掉气泡让其整个空间 充满化成液； 并且除极板上的板耳外其余部分全部泡在化成液中，浸泡 20小时， 使化成液浸透极板和隔棉， 这样在在化成时不发热， 达到化成彻底； A 12V100Ah battery capable of operating at a depth of 6000 meters in the deep sea is made. ABS engineering plastic and polystyrene are prepared at 8: 2 (weight ratio) to prevent material from bursting under pressure. The method is to make a casing of a box-type battery with a wall thickness of 3 mm × length 150 mm × width 95 legs. The casing is divided into a base 1 and an upper cover plate 11. The casing base 1 is evenly divided into 6 cells by partition walls 12 and the bottom surface of the cell. There are raised saddle-shaped saddles 5, and the plates are placed on the saddles 5. The height of the saddles 5 is 50% higher than that of ordinary saddles. The purpose is to help the air bubbles in the battery case to be driven away. The upper cover plate 11 is rectangular and closely matches the housing base 1. On the top surface of the battery upper cover plate 11, there are 6 Φ 10 ιηι normally valve-controlled filling ports 9, and the position of each filling port 9 corresponds to the center position of each cell in the housing base 1. There are two Φ1 bandit exhaust holes 14 on the protruding edge of the port 9, and a hollow pressure-proof seat 15 as shown in FIG. 2 is placed on each liquid-filling port 9, and is sealed and sealed with sealing glue. Seat 15 is made of elastic rubber material, or plastic material, plastic material. Each hollow pressure-proof seat 15 is covered with a Φ outer diameter im X length 600mm X wall thickness 3 Let the rubber tube with reinforcing ribs be used as pressure The outer surface of the buffer balance tube 16 is sealed with epoxy resin, and the end of the tube is made of a sealing plug 17 made of the same material. Closed. A grid and a spacer made of ordinary materials are fixedly arranged in each grid. A negative grid 2 with a positive hexagonal honeycomb network is placed from the first grid, and the positive grid 3 is interposed. The negative and positive grids 2 and 3 A 1.2mm-thick spacer 4 is placed in between, and the main structure of the installed battery is shown in FIG. 1. The thickness of the negative grid 2 is 0.8 bandit, the thickness of the frame is 1.2, and the thickness of the positive grid 3 is 1.2 mm, and the thickness of the frame is L 8mm. The positive electrode grid 3 is coated with lead paste consisting of 100 kg of lead powder, 500 g of graphite, 50 g of short-fiber paper, 12.26 kg of sulfuric acid (25 ° C d = 1.38), and 14 kg of water. Density is 4.2 g / cm 3 ; the negative electrode grid is coated with 100 kg of lead powder, 500 g of barium sulfate, 50 g of staple fiber paper, 8.19 kg of sulfuric acid (25 ° C d-1. 38), water 14 Kilograms of lead paste mixed with a density of 4.3 g / cm 3 . There is no gap between the negative and positive grids 2 and the spacer 3, and so on, and there is a total of 6 negative grids 2, 5 positive grids 3, and 10 spacers 4 in each cell. A lead busbar 6 The positive and negative grids in a grid are connected in parallel, and the positive and negative grids between the grid and the grid are connected in series through a connecting post 10 (not shown), and then connected to the positive and negative posts 7, 8 respectively. The connection method between the grid, the pole, and the connecting post is the same as the normal battery installation method. Then, the lower base of the installed battery is covered with the battery cover 11 with the battery self-regulating structure. The oxygen resin is sealed well, and no ventilation is allowed between each cell. The liquid low-sodium silicon salt prepared in Example 1 is injected into each cell in the tank. It is both a dielectric and a chemical conversion liquid. The salt fullness is filled with the pressure buffer balance tube. When adding the chemical solution to the battery tank, shake the battery tank at a constant speed on a vibration machine with a uniform vibration to remove the air bubbles and fill the entire space with the chemical solution. Rest of plate's ears All soaked in the chemical conversion solution and soak for 20 hours and separated into liquid impregnated cotton pad, so that no heat during the chemical conversion, reaches into complete;
用化成充电机进行通电化成， 如使用 "uc-KGCFD2经济型 40回路充放电 电源"对步骤 4装好的电池通电化成， 化成温度为： 室温； 化成时间： 30-50小 时， 48小时最佳化成电压 2.2V。  Use a formation charger to perform energization. For example, use "uc-KGCFD2 economical 40-circuit charge and discharge power supply" to energize the battery installed in step 4. The formation temperature is: room temperature; the formation time: 30-50 hours, 48 hours is the best Formation voltage is 2.2V.
本实施例制作的蓄电池安装有电池自调压结构， 该电池自调压结构是在蓄 电池上盖每一阀控加液口边缘开有 2个排气孔、 阀控加液口外套中空防压座、 中空防压座与每个排气孔连通， 一端被密封住的压力缓冲平衡管的幵口端包覆 在中空防压座外而组成的电池自调压结构， 由于该压力缓冲平衡管是与蓄电池 内腔连通的， 当蓄电池在深海下使用超过 1 个大气压时， 压力缓冲平衡管可以 压扁一点， 把液体向电池壳内压进， 提高壳内抗压能力。 保持内外压力平衡， 具有压力自调节作用的环保蓄电池。  The battery produced in this embodiment is equipped with a battery self-regulating structure. The battery self-regulating structure is provided with two vent holes on the edge of each valve-controlled filling port on the battery cover, and the valve-controlled filling port jacket is hollow to prevent pressure. A self-regulating structure for a battery composed of a seat and a hollow pressure-proof seat that communicates with each exhaust hole. One end of the sealed pressure-buffering balance tube is covered by the outside of the hollow pressure-proof seat. It is in communication with the internal cavity of the battery. When the battery is used in the deep sea for more than 1 atmosphere, the pressure buffer balance tube can be flattened a little, and the liquid is pushed into the battery case to improve the pressure resistance in the case. An environmentally friendly battery that maintains internal and external pressure balance and has self-regulating pressure.
本实施例制作的在深海下使用的蓄电池具有良好的性能： ( 1 )放电不产生气泡； The battery produced in this embodiment used in the deep sea has good performance: (1) No bubbles are generated during discharge;
(2) 电池壳内灌满液态低钠硅盐电介质是采用磁化工艺制得的， 它既是电 介质又是化成液， 在蓄电池制造工艺中大大地减少工序， 减轻工人的劳动强度； (2) The battery case filled with liquid low-sodium silicon salt dielectric is made by a magnetization process, which is both a dielectric and a chemical fluid, which greatly reduces the number of processes in the battery manufacturing process and reduces the labor intensity of workers;
(3)所灌装电介质需加装的充满度以充满压力缓冲平衡管内为止， 比重是 1. 32， 因此， 该电池在外界较大的压力下电流和电压保持稳定； (3) The filling dielectric needs to be filled to fill the pressure buffer balance tube. The specific gravity is 1. 32. Therefore, the current and voltage of the battery remain stable under a large external pressure;
(4) 该蓄电池可在 -50°C〜+60°C的温度下正常使用， 在深海下温度变化很 大的情况下本发明的深海蓄电池能正常工作， 并且， 放点电压稳定；  (4) The battery can be used normally at a temperature of -50 ° C to + 60 ° C, and the deep-sea battery of the present invention can work normally when the temperature changes greatly in the deep sea, and the discharge point voltage is stable;
(5)从一般的 3〜7C放电能力提高到 30C以上放电能力， 本实施例制做在 深海 6000米下工作的蓄电池恒流放电图如图 4所示； 可以与普通铅酸蓄电池放 电标准比较如下：  (5) The discharge capacity from 3 ~ 7C in general to 30C or more is improved. The constant current discharge diagram of the battery manufactured in this embodiment working at 6000 meters in the deep sea is shown in Figure 4; it can be compared with the discharge standard of ordinary lead-acid batteries. as follows:
3C放电曲线 （本发明的蓄电池） 9. 8分钟电压下降到 10. 5V: 2C放电曲线 （本发明的蓄电池） 24. 6分钟电压下降到 10. 5V;  3C discharge curve (battery of the invention) 9. 8 minutes voltage drops to 10. 5V: 2C discharge curve (battery of the invention) 24. 6 minutes voltage drops to 10. 5V;
1C放电曲线 （本发明的蓄电池） 48分钟电压下降到 10. 5V; 3C放电标准（铅酸蓄电池） 7. 5分钟电压下降到 10. 5V  1C discharge curve (battery of the present invention) Voltage drops to 10. 5V in 48 minutes; 3C discharge standard (lead-acid battery) 7. 5 minutes voltage drops to 10. 5V
2C放电标准（铅酸蓄电池） 21分钟电压下降到 10. 5V  2C discharge standard (lead-acid battery) The voltage drops to 10.5V in 21 minutes
1C放电标准（铅酸蓄电池） 33分钟电压下降到 10. 5 V  1C discharge standard (lead-acid battery) Voltage drops to 10. 5 V in 33 minutes
实施例 3  Example 3
制作一 12V200Ah的深海蓄电池， 其该深海蓄电池的主体结构同实施例 1和 2相同， 区别在于在一个阀控加液口 9凸出的边缘上开有 4个 Φ lmm排气孔 14， 加液口 9上套一个如图 2所示的中空防压座 15， 使中空防压座 15与 4个 Φ lmm 排气孔 14连通，并用封口胶 7密封固定住，中空防压座 15外套一根 Φ躲 14mm X 长度 600mmX 3. 5 mm塑胶管做为压力缓冲平衡管 16， 其接口的外面用环氧树脂 密封， 该管的末端用密封胶封闭。  A 12V200Ah deep-sea battery is produced. The main structure of the deep-sea battery is the same as that of Examples 1 and 2. The difference is that four Φ lmm exhaust holes 14 are opened on the protruding edge of a valve-controlled filling port 9 to add liquid. A hollow pressure-proof seat 15 as shown in FIG. 2 is put on the mouth 9 so that the hollow pressure-proof seat 15 communicates with four Φ lmm exhaust holes 14 and is sealed and fixed with sealing glue 7. A hollow pressure-proof seat 15 is sheathed. Φ hide 14mm X length 600mmX 3. 5 mm plastic tube as pressure buffer balance tube 16, the outside of its interface is sealed with epoxy resin, and the end of the tube is sealed with sealant.
实施例 4  Example 4
制作一具有 10小时率 12V38Ah的、 在 6000米工作的深海蓄电池， 该电池 尺寸为长 197 mm X宽 65 mm X高 172 mm ， 该深海蓄电池的主体结构和电解 液、 化成液同实施例 1和 2相同， 区别在于在每个阀控加液口 9凸出的边缘上 各开有 2个 4> lmm排气孔 14， 该管的末端用密封胶封闭。 所制得的该深海蓄电 池具有放电无酸雾， 恢复性能良好； 电容量大于 40Ah。  A deep-sea battery with a 10-hour rate of 12V38Ah and operating at 6000 meters was produced. The size of the battery was 197 mm in length X 65 mm in width X 172 mm in height. The main structure of the deep-sea battery, the electrolyte, and the formation solution were the same as those in Examples 1 and 1. 2 is the same, the difference is that two 4> lmm exhaust holes 14 are opened on the protruding edge of each valve-controlled filling port 9, and the end of the tube is closed with a sealant. The prepared deep-sea storage battery has no acid mist discharge and good recovery performance; the capacity is greater than 40Ah.

Claims

权 利 要 求 Rights request
1. 一种适于深海作业中使用的耐压环保蓄电池， 包括： 电池壳体、 正、 负板栅组、 隔棉、 汇流板、 连接柱、 电介质、 化成液， 其特征是： 还包括在上 盖板的阀控加液口上开有排气孔， 并在每一阀控加液口上安装电池自调压结构， 所述的电池壳体是由采用 ABS工程塑料与耐酸的软塑料以 8 : 2重量份配料， 经 常规方法制成壁厚 3〜4. 5mm的， 分为上盖板、 下底座的箱式电池壳体； 下底座 内设置的隔墙分为格， 一般格数为 2伏一格； 格内底面上有凸起筋状的鞍子， 极板安放在鞍子上， 鞍子的高度比一般蓄电池内的鞍子高 50%; 1. A pressure-resistant and environmentally-friendly storage battery suitable for use in deep sea operations, comprising: a battery case, a positive and negative grid, a spacer, a bus bar, a connecting post, a dielectric, and a chemical conversion fluid, characterized in that: A vent hole is opened on the valve-controlled liquid-filling port of the upper cover plate, and a battery self-regulating structure is installed on each valve-controlled liquid-filling port. The battery case is made of ABS engineering plastic and acid-resistant soft plastic. : 2 parts by weight, made by conventional methods with a wall thickness of 3 ~ 4.5mm, which is divided into a box battery case with an upper cover and a lower base; the partition wall provided in the lower base is divided into cells, and the general number of cells is 2 volts per grid; there are raised saddles on the bottom surface of the grid, and the plates are placed on the saddles, and the height of the saddles is 50% higher than that of ordinary saddles in batteries;
所述的板栅是用铅或铅合金制成正六角形蜂窝网状的板栅， 大小以刚好装 入箱式电池的壳体下底座内为宜，负板栅的边框比边框内的蜂网部分要厚 02. 〜 0. 6， 正板栅的边框比边框内的蜂网部分要厚 0. 3〜0. 8， 并且正、 负板栅上涂 有铅膏； 其中负、 正板栅与隔棉相间安装在电池壳体底座内的每一格内， 相邻 板栅之间不留空隙， 同一格内的正、 负板栅用汇流板各自通过板耳并联起来， 格与格之间的正、 负板栅分别通过连接柱串联连接， 再连接到正、 负极柱上， 电池下底座上盖好安装有电池自调压结构的壳盖， 再用环氧树脂密封固定； 电 池壳内每一格灌满既是电介质又作为化成液的采用磁化；艺制得的液态低钠硅 盐， 所灌装液态低钠硅盐的充满度以充满压力缓冲平衡管内为止； 并除极板上 的板耳外其余部分全部泡在化成液中。  The grid is made of lead or lead alloy with a regular hexagonal honeycomb mesh grid. The size of the grid is preferably inserted into the lower base of the casing of the box battery. The frame of the negative grid is larger than the honeycomb in the frame. The part should be thicker from 02. to 0.6, and the frame of the positive grid is thicker than that of the honeycomb part within the frame by 0.3 to 0.8, and the positive and negative grids are coated with lead paste; It is installed in each cell in the base of the battery casing with spacers. There is no gap between adjacent grids. The positive and negative grids in the same grid are connected in parallel by plate ears. The positive and negative grids are connected in series by connecting posts, and then connected to the positive and negative poles. The lower base of the battery is covered with a cover that is equipped with a battery self-regulating structure, and then sealed with epoxy resin. Each cell inside is filled with magnetization that is both a dielectric and a chemical conversion liquid. The liquid low-sodium silicon salt prepared by the art is filled until the filling of the liquid low-sodium silicon salt fills the pressure buffer balance tube; and the electrode plate is removed. The rest of the plate's ears are all soaked in the chemical solution.
2. 按权利要求 1所述的适于深海作业中使用的耐压环保蓄电池， 其特征 是： 所述的电池自调压结构是在电池上盖板顶面上的阀控加液口凸出的边缘上 开有排气孔， 加液口外套一个中空防压座， 中空防压座与排气孔连通， ***用 密封胶密封固定住， 中空防压座外密封包覆一根弹性材料制做的压力缓冲平衡 管， 该管的长短按蓄电池使用时的海深决定， 该管的末端密封住。  2. The pressure-resistant and environmentally-friendly storage battery suitable for use in deep sea operations according to claim 1, characterized in that: the battery self-regulating structure is a valve-controlled filling port protruding on the top surface of the battery cover plate. There is a vent hole on the edge, a hollow pressure-proof seat is placed on the filling port, the hollow pressure-proof seat communicates with the exhaust hole, the periphery is sealed with a sealant, and the outer part of the hollow pressure-proof seat is covered with an elastic material. The pressure buffer balancing tube is made, the length of the tube is determined by the sea depth when the battery is used, and the end of the tube is sealed.
3.按权利要求 1所述的适于深海作业中使用的耐压环保蓄电池，其特征是: 所述的耐酸软塑料包括： 聚苯乙烯、 聚乙烯和其它具有弹性的塑料。  The pressure-resistant and environmental-friendly storage battery suitable for use in deep sea operations according to claim 1, wherein the acid-resistant soft plastic comprises: polystyrene, polyethylene, and other plastics having elasticity.
4.按权利要求 2所述的适于深海作业中使用的耐压环保蓄电池，其特征是: 所述的压力缓冲平衡管的长度按水深一米管长 10公分，该管用橡胶管、乳胶管、 洗衣机用的胶管、 带有加强筋的煤气用的胶管， 和其它弹性材料制做的。  4. The pressure-resistant and environmental-friendly storage battery suitable for use in deep-sea operations according to claim 2, characterized in that: the length of the pressure buffer balance pipe is 10 cm in length at a depth of one meter, and the pipe is made of rubber pipe, latex pipe , Rubber hoses for washing machines, rubber hoses with reinforcing ribs, and other elastic materials.
5.按权利要求 2所述的适于深海作业中使用的耐压环保蓄电池，其特征是: 所述的压力缓冲平衡管的另一端用同种材料作的塞子密封住、 用胶密封住或采 物理办法密封住。 The pressure-resistant and environmental-friendly storage battery suitable for use in deep sea operations according to claim 2, characterized in that: the other end of the pressure buffer balance pipe is sealed with a plug made of the same material, sealed with glue, or Pick Physically sealed.
6.按权利要求 1所述的适于深海作业中使用的耐压环保蓄电池，其特征是： 所述的液态低钠硅盐是采用磁化工艺制得的：  The pressure-resistant and environmental-friendly storage battery suitable for use in deep-sea operations according to claim 1, characterized in that: said liquid low-sodium silicon salt is made by a magnetization process:
a.取含 40〜60wt% 5:102的硅溶胶 5~15重量份； a. Take 5 ~ 15 parts by weight of silica sol containing 40 ~ 60wt% 5:10 2 ;
b.边搅拌边加入水到步骤 1的硅溶胶中， 加入 15〜25重量份水， 当波美 浓度为 0. 65〜0. 85% QBe，时不再加入水为止； b. While stirring, add water to the silica sol of step 1, add 15 ~ 25 parts by weight of water, when the Baume concentration is 0.65 ~ 0. 85% Q Be, when no more water is added;
c向上述步骤 2所得的产物中加入无机酸混合， 边加入无机酸边测量该混 合物的 pH值， 直到 pH值为 1〜4时停止加入；  c Add an inorganic acid to the product obtained in the above step 2 and measure the pH value of the mixture while adding the inorganic acid, and stop adding until the pH value is 1-4;
d.把上述步骤 3的混合物放到一个具有 1000〜6000高斯的磁场进行磁化 5~10分钟；  d. Put the mixture in step 3 above into a magnetic field with 1000 ~ 6000 Gauss for magnetization for 5 ~ 10 minutes;
e.将上述步骤 4磁化后的混合物进行搅拌， 其搅拌包括^工搅摔或机械搅 拌， 其机械搅拌速度为 700〜1400转 /分， 搅拌 5〜10分钟， 当粘度小于 0. 02 泊 (mPas)时停止搅拌， 制得粘度小于 0. 02泊的蓄电池用液态低钠硅盐；  e. The above magnetized mixture of step 4 is stirred, and the stirring includes mechanical stirring or mechanical stirring, and the mechanical stirring speed is 700 to 1400 rpm, and the stirring is performed for 5 to 10 minutes, when the viscosity is less than 0.02 poise ( mPas) when the stirring was stopped to obtain a liquid low sodium silicon salt for a battery having a viscosity of less than 0.02 poise;
7.按权利要求 1所述的适于深海作业中使用的耐压环保蓄电池，其特征是- 所述的正极板栅铅膏： 由铅粉 100公斤、石墨 500克、短纤纸 50克、硫酸 12. 26 公斤、 水 14公斤混合而成， 铅膏密度为 4. 2克 /cm3; The pressure-resistant and environmental-friendly storage battery suitable for use in deep sea operations according to claim 1, characterized in that-the positive grid grid lead paste: 100 kg of lead powder, 500 g of graphite, 50 g of staple fiber paper, Mixing 12.26 kg of sulfuric acid and 14 kg of water, the density of lead paste is 4.2 g / cm 3 ;
所述的负极板铅膏： 由铅粉 100公斤、 硫酸钡 500克、 短纤纸 50克、 硫 酸 8. 19公斤、 水 14公斤混合而成， 铅膏密度为 4. 3克 /Cffl3。' The negative plate lead paste: a mix of 100 kg of lead powder, 500 g of barium sulfate, 50 g of staple fiber paper, 8.19 kg of sulfuric acid, and 14 kg of water. The density of the lead paste is 4.3 g / C ffl 3 . '
8.按权利要求 3所述的适于深海作业中使用的耐压环保蓄电池，其特征是: 所述的磁场是用磁性材料制作的具有 1000〜6000高斯的圆桶。  The voltage-resistant and environmental-friendly storage battery suitable for use in deep-sea operations according to claim 3, wherein the magnetic field is a circular drum made of magnetic material and having a range of 1000 to 6000 Gauss.
PCT/CN2001/001224 2001-06-12 2001-08-09 A storage battery resistant to pressure and beneficial to environmental protection, which is suitable for being used in deep sea WO2002101868A1 (en)

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