WO2001095422A1

WO2001095422A1 - The recycling battery

Info

Publication number: WO2001095422A1
Application number: PCT/CN2001/000552
Authority: WO
Inventors: Yang Xu; Qiulei Liu
Original assignee: Yang Xu; Qiulei Liu
Priority date: 2000-04-12
Filing date: 2001-04-10
Publication date: 2001-12-13
Also published as: CN1421056A; CN1219339C; WO2001095422A8; AU2001267264A1

Abstract

The present invention provides a recycling battery including a feeding means, a battery stack and a releasing means. A certain amount of metal grains and electrolyte are added into every cell of the battery by feeding means, so the battery can operate normally. Since the waste liquid is released from the releaing means and the new electrolyte and metal grains were added when output voltage or current of the battery is lower than the rating, the battery can rework and achieve charge-discharge-charge recycling. The battery having the characters of quick charging, long discharging period and high capacity can be obtained. The waste electrolyte can be reused by reduction. In other words, there is no pollution. This recycling battery becomes a new source.

Description

Recycling battery

Technical field

The present invention relates to a battery, and particularly to a battery capable of being recycled. Background technique

At present, there are many types of dry batteries and rechargeable batteries on the market. However, they all have the problems of small battery capacity, short continuous discharge time, and high manufacturing cost. In addition, for rechargeable batteries, there are also disadvantages that AC power must be used for charging and the charging waiting time is long, which brings a lot of inconvenience to the use in areas without AC power, such as rural areas and the wild. Summary of invention

In view of the above problems, the inventor finally completed the present invention through careful research.

The present invention provides a circulating battery, which includes a charging device, a battery pack, and a discharging device, wherein the charging device includes a feeding port for adding metal particles, a charging port for adding an electrolyte, and a surplus An overflow pipe from which the electrolyte is discharged; the battery pack includes at least one unit battery; and the discharging device is provided at a lower portion of the battery. This kind of battery is used to randomly and regularly add metal particles and electrolyte to make the battery work normally. When the output voltage or current of the battery is lower than the rated value, the waste liquid in the battery is discharged, and the new electrolyte is replenished through the liquid adding tank, and After adding new metal particles through the loading bin, the battery can work again, and if the electrolyte level exceeds a certain amount, it will flow out through the overflow pipe. The recovered spent electrolyte can be reused through reduction reaction, so that the battery can be recycled.

The cyclic battery provided by the present invention is based on an electrochemical theory, and under the above-mentioned guiding ideology, different structural designs can be implemented according to actual use conditions.

According to the technical solution of the present invention, the unit battery is provided with at least one positive electrode plate and one negative electrode current collector, a separator is provided between the positive electrode plate and the negative electrode current collector, and metal particles and the negative electrode current collector are provided. In contact, each single cell is assembled by a battery case.

The positive electrode plate is made in the order of a catalyst layer, a black powder layer, a positive electrode current collector network, and a black powder layer from the inside to the outside, and the outer black powder layer is in contact with air or oxygen.

The circulating battery provided by the present invention may include two types of products according to the overall structure and working process. In the first type, the positive electrode plate, the separator, and the negative electrode current collecting net are sequentially brought into contact with each other and pressed into one body. There is a screen, and the screen is located on the upper part of the discharging device. Metal particles and electrolyte are added to the single battery from the charging bin and the liquid adding bin, respectively. The reaction starts and the battery is powered. When the output voltage or current is lower than the standard value, the waste is discharged from the control valve of the discharge port according to the prompt. At the same time, when the electrolyte or metal particles are replaced or added, the battery can work again to achieve cyclic discharge.

In the second type, an electrolyte circulation device is added to make the electrolyte circulate during the power supply process, with the supplementation of metal particles and the electrolyte, and the cleaning of waste liquid and residues, so as to obtain a constant discharge power and realize the circulation type. Discharge. Detailed description of the invention

The circulating battery provided according to the present invention includes a charging device, a battery pack and a discharging device, wherein the charging device includes a feeding port for adding metal particles, a feeding port for adding an electrolyte, and an unnecessary electrolytic device. Liquid discharge overflow pipe; the battery pack includes at least one single battery; the discharging device is arranged at the lower part of the battery

The single battery is provided with at least one positive plate and a negative current collector. A separator is provided between the positive plate and the negative current collector. Metal particles are in contact with the negative current collector. The box is assembled, and the positive and negative electrodes on the outside of the single cell are connected in series or in parallel with each other to form a battery pack. '' The positive electrode plate in the unit cell is made from the inside to the outside in the order of catalyst layer, black powder layer, positive current collector, and black powder layer. The outer black powder layer is in contact with air or oxygen. '

The metal particles in the battery of the present invention can be made of lithium, sodium, calcium, aluminum, magnesium, zinc, iron, cadmium, and have regular or irregular geometry such as granular or flakes with a large surface area, such as hollow or Solid cylinders, hollow or solid cones, hollow or solid spheres, hollow or solid cuboids, and shavings, etc.

The positive electrode current collector network and the negative electrode current collector network are made of a conductive material, and preferably the negative electrode current collector network is honeycomb, circular, prismatic, stripe, rectangular, or other irregular shapes.

According to a solution of the present invention, the positive electrode plate, the separator, and the negative electrode current collecting net are sequentially brought into contact with each other and pressed into an integrated body, or the negative electrode current collecting net is packed into a single cell in a strip shape. Air baffle that controls the flow of air through the positive plate. The feeding device is provided with a combined feeding bin, a large shell cover and a casing. The single battery is connected to form a battery pack through the feeding bin, the large shell cover and the casing. A feeding opening and a quantitative quantity of metal particles are provided below the feeding bin. Control device.

Wherein, the quantitative control device is a drawable drawing plate, and the drawing plate is provided with a hole or a slot corresponding to a single battery, or a whole plate.

Alternatively, the quantitative control device is a swing door controlled by an elastic hinge.

According to the preferred solution of the present invention, the discharge device includes a battery waste liquid discharge port and a liquid discharge tank, the waste liquid discharge port includes a waste liquid storage tank, and a control valve is provided at the lower end pipe joint. When it is necessary to replace the reaction material, the battery waste liquid that reaches the waste liquid storage tank can be discharged to the drain tank through the control valve; _i: Medium. The control valve may be a manual valve or an electric valve, or it may be composed of a U-shaped chuck and a clamping seat matched with it.

_; According to the present invention a second type of battery cycles, increased electrolyte circulation means, a circulation pump which may be utilized by the work itself energy, infusion tube, spraying the electrolytic solution to the cell and storage electrolysis spray pipe. It consists of a liquid storage tank. The circulation pump is set on the liquid storage tank. The infusion tube is drawn from the storage tank and connected to the shower tube. The negative current collector network is set on the surface of the unit battery that is perpendicular to the positive plate and the diaphragm. And partly placed in the metal particles, and the lower part is a screen that can block the metal particles.

According to this embodiment of the present invention, the electrolyte is driven into the battery through the infusion tube and sprayed into the battery through the infusion tube under the driving of the circulation pump, and the circulation flow is realized.

The overflow pipe communicates with the liquid storage tank, and the excess electrolyte is returned to the liquid storage tank.

Optionally, a valve for controlling the discharge of waste liquid may be provided at the lower liquid outlet of the battery, preferably Porcelain valve, or the liquid storage tank is set on one side of the battery, and a liquid return pipe at the bottom of the battery is connected with the liquid storage tank.

According to the above principle, by adopting the above technical solution, the circulating battery of the present invention can add the electrolyte and metal particles randomly or at a time, and at the same time, the waste liquid can be discharged through the valve, thereby realizing the battery power-charging-power cycle.

In addition, the cyclic battery of the present invention can be randomly or regularly added due to the metal particles and the electrolyte, thereby achieving the purpose of long continuous battery discharge time, large capacity, stable discharge voltage, and short charging time, which can provide no AC power to rural areas and the wild. The use of the area brings convenience.

In addition, the waste liquid of the recycle battery of the present invention can be recycled and regenerated, so that the metal particles can be reused, which saves energy, protects the environment, and reduces costs.

Table 1 shows the results of comparison between the related parameters of the circulating battery of the present invention and the existing batteries.

Table 1

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic structural diagram of a single battery in a first type battery of the present invention.

FIG. 2 is a cross-sectional view taken along A-A in FIG. 1.

FIG. 3 is a schematic diagram of a half-section structure of an embodiment of a battery pack (12 groups) of the first type of battery of the present invention.

FIG. 4 is a cross-sectional view taken along BB of FIG. 3. FIG. 5 is a plan view of FIG. 4.

FIG. 6 is an enlarged schematic view of a portion C in FIG. 3.

FIG. 7 is a schematic diagram of a half-section structure of another embodiment of the battery pack of the first type of battery of the present invention.

Fig. 8 is a sectional view taken along the line D-D in Fig. 7.

FIG. 9 is an enlarged schematic view of a portion E in FIG. 7.

FIG. 10 is a schematic structural diagram of an embodiment of a battery discharging device according to the present invention.

FIG. 11 is an enlarged schematic view of a portion H in FIG. 2.

FIG. 12 is a structural diagram of a second type of battery of the present invention.

FIG. 13 is a structural principle diagram of the battery cell shown in FIG. 12 according to the present invention.

FIG. 14 is an enlarged schematic view of part I in FIG. 12.

FIG. 15 is a schematic diagram of a battery structure according to another embodiment of the second type of the present invention.

FIG. 16 is an enlarged schematic view of a Q portion in FIG. 15.

FIG. 17 is a structural principle diagram of the single cell of the embodiment shown in FIG. 15.

Fig. 18 is a plan view of the battery of the embodiment shown in Fig. 15.

FIG. 19 is a schematic structural diagram of a battery according to another embodiment of the second type of the present invention. FIG. 20 is an enlarged schematic view of a Z portion in FIG. 19.

FIG. 21 is a schematic diagram of a unit structure of the battery of the embodiment of FIG. 19. FIG. '

Figure 22 is the battery discharge curve of the present invention (showing the relationship between voltage and time at 17A discharge). The best way to implement the invention

Referring to Figs. 1-6, the circulating battery of the present invention is composed of a charging device at the upper part, a battery pack at the middle and a discharging device at the lower part. The feeding device includes a feeding port 29, a liquid feeding port 30 and an overflow pipe 18, the feeding port 29 is used for quantitative or non-quantitative addition of metal particles 17, and the liquid feeding port 30 is used for quantitative or non-quantitative addition of the electrolyte, and the overflow tube 18 can cause excess electrolyte to overflow into the overflow tank 28. The battery pack may include one or more single cells 6, each of which is assembled by a battery case 13, and the positive and negative electrodes on the outside of the single cell 6 are connected in series or in parallel with each other to form a battery pack, and pass through the charging compartment 3 The large shell cover 4 and the shell 5 are connected.

In the structure diagram shown in FIG. 1, the right side is a view with metal particles 17, and the left side is a view after removing the metal particles 17. The metal particles 17 may be made of lithium, sodium, calcium, aluminum, magnesium, iron, cadmium, etc. It is made of metal, and its shape is preferably regular or irregular geometry such as granular or flakes with a large surface area, such as hollow or solid cylinders, hollow or solid cones, hollow or solid spheres, hollow or solid cuboids, and shavings. Flaky and so on. As shown in FIG. 1 and FIG. 2, a left-right symmetrical positive plate 14, a separator 15, and a negative current collecting network 16 are installed on the battery case 13, with metal particles 17 in the middle, and a screen 21 at the bottom of the metal particles 17. The plate 14 is formed by pressing the catalyst layer, the black powder layer, the positive current collecting network 27, and the black powder layer in plane contact in order, and the outer black powder layer is in contact with the air (oxygen) outwards. Made of electrical conductors. An anode of the positive electrode plate 14 is connected to the positive electrode 33 of the box body 13, and a negative electrode current collector network 16 in a stripe shape is connected to the negative electrode 32. Figures 1 and 2 show the structure of a single cell. • According to the actual situation, it can also be used as a single battery. _:: An enlarged schematic view of the display 11, the positive electrode plate 14, separator 15 and negative electrode collector 16 in contact with drift is integrally formed by cold or hot.

The discharge device includes a waste liquid storage tank 34 and a valve 11. The waste liquid storage tank 34 is located in the lower part of the battery box 13 and has a funnel shape. The bottom of the tank is provided with a pipe joint 22 and a controllable valve 11. The outlet of the pipe joint 22 is correspondingly placed.液槽 31。 The liquid tank 31.

Fig. 3, Fig. 4, Fig. 5 and Fig. 6 show specific embodiments of a battery composed of 12 single cells, which include a charging device, a battery pack and a discharging device.

Among them, in the feeding device, the feeding bin 3, the shell cover 4 and the shell 5 are connected as a whole. The feeding bin 3 is provided with a feeding lid 1 above, and there is a drawable drawing plate 7 below, and the drawing plate 7 is provided with a corresponding hole. As shown in FIG. 6, when the drawing plate 7 moves a certain distance, the metal particles 7 in the feeding bin 3 can fall into the respective single cells 6. In addition, the drawing plate 7 can also be a whole plate, all Withdrawal can also achieve quantitative feeding. There is a liquid adding compartment 2 on the right side of the battery, which can be used to add electrolyte with or without quantitative. Battery An overflow pipe 18 is provided on the left side to allow excess electrolyte to flow out. Air baffles 26 are provided on the left and right inner sides of the battery, which can control the flow of air (oxygen) through the positive plate 14 to adjust the heat dissipation performance inside the discharge battery, or turn off the air (oxygen) to stop discharging. '

The charging bin 3, the cover 4 and the casing 5 are connected to a plurality of single cells 6, as shown in FIG. 3. The left side is a view after the metal particles 17 are removed, and the right side is a view with the metal particles 17. The metal particles 17 are hollow cylinders, and the negative electrode current collector network 16 has a honeycomb shape (or a regular shape such as a circle, a prism, a strip, or a rectangle, or an irregular network or a nano shape). The unit cells 6 may be connected in series or in parallel.

In the discharge device, a funnel-shaped waste storage tank 34 has 11 pipe joints at the lower end, which are provided with electric control valves 10, and the lower end of the pipe joint 22 is connected to the drain pipe 9. The same is the difference, in that: each of the feeding positions below the feeding bin 3 in the feeding device is provided with a rotary door 19, which is controlled by the elastic hinge 20, so that the metal particles 17 can be quantitatively added (as shown in FIG. 9): In the material device, the valve 11 uses a manual valve or an electric valve. In a battery pack, an air baffle is used. '26 The amount of contact between the positive plate 14 and air (oxygen) is controlled to achieve the purpose of controlling discharge.

FIG. 10 is a schematic structural diagram of another valve 11. A hose 2.3 is connected to the pipe joint 22. A U-shaped chuck 25 and a corresponding movable clamp seat 24 are provided on both sides of the hose. In cooperation with the clamp seat 24, the hose 23 is clamped, and the flow is cut off. The clamp base 24 can also be fixed, and the purpose of interrupting the flow or discharging the waste liquid can be achieved by moving the clamp head 25. In addition, the chuck 25 and the chuck seat 24 can also hold the hose 23 in a flat plane, thereby acting as a valve.

The battery structure of the second type of the present invention shown in FIG. 12 and FIG. 13 has an electrolyte circulation device compared with that described above, which is composed of a circulation pump 36, an infusion tube 37, and a single battery 6 that can operate with its own electrical energy. The circulation pipe 36 is provided on the liquid storage tank 39, and the infusion tube 37 is led out from the liquid storage tank 39 and is connected to the spray tube 38. The current collecting network 16 is provided on the surface of the single cell 6 that is perpendicular to the positive electrode plate and the separator 15 and is partially inserted into the metal particles 17 (the portion is in a strip shape). The lower part is a screen that can block the metal particles. The flowing electrolyte is separated from the metal particles without causing clogging. Compared with the previously listed battery In addition, the feed bin 3 and the air baffle 26 are removed, and a pump 36, an infusion pipe 37, a spray pipe 38, and a liquid storage tank 39 are added.

The pump 36 provided with the battery can use its own electric energy to send the electrolyte in the liquid storage tank 39 to the spray pipe 38 through the infusion pipe 37 (as shown in FIG. 14), and the spray pipe 38 is directed to the single battery 6 Spraying, the electrolyte circulates in the battery under the driving of the pump 36, the flow direction is shown in FIG. 13, and finally flows back to the liquid storage tank 39 through the overflow pipe 18. It is then sent into the battery through the infusion tube 37 and the shower tube 38, and the cycle is repeated until the output voltage or current is lower than the rated value. At this time, the waste liquid can be discharged, and new electrolyte and new metal particles can be replenished. In addition, during use, metal particles can be replenished to the single cell 6 at regular or irregular intervals to obtain a constant discharge power. Since the electrolyte flows in the battery, it helps to derive heat in a balanced manner. In addition, the lower part of the battery is also provided with a valve for draining waste liquid. In this embodiment, the valve is preferably a porcelain valve 35. In this way, the porcelain valve switch 35 on the lower part of the battery is periodically opened to remove the residue in the single battery 6. Ensure that the electrolyte can flow smoothly.

Referring again to another embodiment shown in FIG. 15, FIG. 16, FIG. 17, and FIG. 18, the overflow pipe 18 communicates with the liquid storage tank 39 through the external liquid receiving pipe 41. The electrolyte flows through the overflow pipe 18 to the liquid receiving pipe 41 during the circulation process, and then flows back to the liquid storage tank 39 through the liquid receiving pipe 41 to complete a cycle, so that the overflow pipe 18 can be hidden.

Figure 19, Figure 20, and Figure 21 show another embodiment design of this type of battery. A liquid storage tank 39 is provided on one side of the battery, and a liquid return pipe 40 at the bottom of the battery is in communication with the liquid storage tank 39. The electrolyte is sprayed from the shower tube 38 to the single cell 6 and flows directly from the top to the liquid discharge tank 31, and then flows back to the liquid storage tank 39 from the liquid return pipe 40. The liquid storage tank 39 is located on the battery side, The valve 11 is connected, so the electrolyte in the battery and the electrolyte in the reservoir are always in communication. Experimental example

A battery pack consisting of 12 single cells with a rated power of 200W. Add 200 ~ 250g of homemade zinc particles, 200 ~ 230ml of 45% potassium hydroxide (K0H) solution to the inner cavity of each single cell. Adopt Inverter with 80% inverter power, 70W inductive load and 100W resistive load (170W in total) —group, first measure the no-load voltage of the battery, and then add the load to connect the battery line, each cycle separately Measure the voltage and current of the battery pack and the single cell at an interval of 1 hour, record the data, and plot the discharge curve with time as the abscissa and output voltage as the ordinate, as shown in Figure 22. The experimental results are as follows:

Weight: 7Kg

No-load voltage: 17.5V

Rated voltage: 12. 5V

Capacity:> 1800W-h

Rated power:〉 2 caps

Discharge time:> 8h

Charging time: l Omin

It can be seen from the above practical results that the continuous-type battery of the present invention has a long continuous discharge time, a large capacity, a stable discharge voltage, and a short charging time.

Claims

Claim

1. A circulating battery, which is provided with positive and negative electrodes and is equipped with metal particles, which is characterized by comprising a feeding device, a battery pack and a discharging device, wherein the feeding device includes a feeding port for adding metal particles A liquid adding port for adding an electrolytic solution and an overflow pipe for discharging an excess of the electrolytic solution; the battery pack includes at least one single battery; and the discharging device is arranged at a lower part of the battery.

2. The cyclic battery according to claim 1, characterized in that: the unit battery is provided with at least one positive plate and a negative current collecting net or current collecting bar, the positive plate and the negative current collecting net or A separator is provided between the current collecting bars, and the metal particles are in contact with the negative electrode current collecting network or the current collecting bars, and each single cell is assembled by a battery case.

3. The cyclic battery according to claim 2, wherein the positive electrode plate is made from the inside to the outside in the order of a catalyst layer, a black powder layer, a positive current collector network, and a black powder layer, and the outer black powder layer and Contact with air or oxygen.

4. The cyclic battery according to claim 1, characterized in that: the positive electrode plate, the separator and the negative electrode current collecting net or current collecting strip are sequentially brought into contact with each other and pressed into a single body. .

5. The cyclic battery according to claim 4, wherein a sieve is provided under the metal particles, and the sieve is located at the upper part of the discharging device. '

6. The cyclic battery according to claim 1-5, characterized in that: the charging device is provided with a charging chamber, a large shell cover and a casing integrated into one, and the single battery passes the charging chamber, the large shell cover and the casing. The body is connected to form a battery pack, and a feeding opening for metal particles and a quantitative control device are arranged below the feeding silo.

7. The circulating battery according to claim 6, characterized in that: the quantitative control device is a drawable drawing plate, and the drawing plate is provided with a hole or a slot corresponding to the single battery, or a piece The whole board.

8. The cyclic battery according to claim 6, wherein the quantitative control device is a rotary door controlled by an elastic hinge.

9. The ring battery according to claim 6, wherein the discharging device comprises a battery waste liquid discharge port and a liquid discharge tank, the waste liquid discharge port includes a waste liquid storage tank, and a lower end pipe joint is provided at the There are control valves. 10. The cyclic battery according to claim 9, wherein the control valve is a manual valve or an electric valve.

11. The cyclic battery according to claim 9, wherein the valve is composed of a U-shaped chuck and a clamping seat matched with the clevis.

12. The cyclic battery according to claim 6, wherein the left and right inner sides of the unit battery are provided with air baffles capable of controlling the air flow through the positive plate.

13. The circulating battery according to claim 1-3, characterized in that: the circulating battery is further provided with an electrolyte circulation device, which is composed of a circulation pump, an infusion tube, and a single battery which can operate with its own electric energy. The spray pipe for spraying the electrolyte is composed of a storage tank for storing the electrolyte. The circulation pump is arranged on the storage tank, and the infusion pipe is led out from the storage tank and connected to the spray pipe.

14. The cycle-type battery according to claim 13, wherein the negative electrode current collecting network is provided on the surface of the single cell perpendicular to the positive electrode plate and the separator, and is partially placed in the metal particles, and the lower part is a barrier metal Granulated sieve.

15. The circulating battery according to claim 13, 14, characterized in that the overflow pipe is in communication with the liquid storage tank. '

16. The circulating battery according to claim 15, wherein the overflow pipe communicates with the liquid storage tank through a liquid connecting pipe of an external device.

17. The cyclic battery according to claim 13, 14 or 13, characterized in that: the lower liquid outlet of the battery is provided with a valve for controlling the discharge of waste liquid.

18. The circulating battery according to claim 17, wherein the valve is a porcelain valve.

19. The circulating battery according to claim 13, wherein the liquid storage tank is disposed on one side of the battery, and a liquid return pipe at the bottom of the battery is connected to the liquid storage tank.

20. The cyclic battery according to claim 1, wherein the metal particles are made of lithium, sodium, calcium, aluminum, magnesium, zinc, iron, and cadmium.

21. The cyclic battery according to claim 1, 20, wherein the metal particles are geometric bodies with a large surface area. 11. The cyclic battery according to claim 2, wherein the positive electrode current collector network and the negative electrode current collector network are made of a conductive material.

23. The cyclic battery according to claim 2, 22, wherein the negative electrode current collecting network is a honeycomb, a circle, a prism, a strip, a rectangle, or an irregular shape.

24. The cyclic battery according to claim 1, wherein a plurality of single cells are connected in series or in parallel.