Zinc rechargeable battery

Abstract

The formation of dendrites causes a short circuit between the positive and negative electrodes. [Solution] The battery container 101 contains a positive electrode material 106, a negative electrode material 103 containing zinc, a separator 109 having a conductive layer 110, and an electrolyte 108 that permeates the positive electrode material 106 and the negative electrode material 103. A positive terminal 107 is connected to the positive electrode material 106, a negative terminal 104 is connected to the negative electrode material 103, and a conductive terminal 111 is connected to the conductive layer 110. Dendrites generated from the negative electrode material 103 in contact with the conductive layer 110 are severed by applying a current between the negative terminal 104 and the conductive terminal 111.

Description

[Technical Field]

[0001] This invention relates to zinc (secondary) batteries, including nickel-zinc secondary batteries, silver-zinc secondary batteries, manganese-zinc secondary batteries, and zinc-air secondary batteries, as well as a battery unit using the zinc (secondary) battery of the present invention, a control method for the battery unit, and a battery device.

[0002] This invention relates to an electrolyte and battery structure that improve the efficiency and characteristics of a zinc secondary battery, and also to a structure, method, method of use, and driving method for preventing short circuits between the negative and positive electrodes of a zinc (secondary) battery due to dendrites. The invention also relates to a zinc secondary battery, a motor drive device having a battery unit, and an electric vehicle having a zinc secondary battery as a power source. [Background technology]

[0003] In zinc secondary batteries, there is a need for technology to prevent short circuits caused by zinc dendrites. Patent document 1 (Japanese Patent Publication No. 6-196199) proposes the suppression of dendrites by a separator in nickel-zinc batteries. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 6-196199 [Overview of the project] [Problems that the invention aims to solve]

[0005] Zinc batteries, such as nickel-zinc rechargeable batteries, have an extremely high theoretical capacity density, approximately five times that of nickel-cadmium rechargeable batteries, 2.5 times that of nickel-metal hydride rechargeable batteries, and 1.3 times that of lithium-ion batteries, and also have the advantage of being made from inexpensive raw materials.

[0006] However, zinc secondary batteries have a problem in that during charging, the zinc constituting the negative electrode generates dendritic crystals called dendrites 205, and these dendrites 205 can pierce the separator 109 and short-circuit the negative and positive electrodes. Furthermore, due to issues with the electrolyte, there is a problem in that efficiency tends to decrease easily. [Means for solving the problem]

[0007] The zinc secondary battery of the present invention comprises a positive electrode material, a negative electrode material containing zinc, a separator having a conductive layer, an electrolyte that permeates the positive electrode material and the negative electrode material, and a power supply device that applies current or voltage between the negative terminal and the conductive terminal, wherein the positive terminal is connected to the positive electrode material, the negative terminal is connected to the negative electrode material, and the conductive terminal is connected to the conductive layer.

[0008] The zinc secondary battery of the present invention uses NaClO4 as the electrolyte, with NaOH added. In one embodiment, a perchlorate aqueous solution is added to the alkaline electrolyte NaOH. Examples of perchlorate aqueous solutions include lithium perchlorate (LiClO4) aqueous solution, sodium perchlorate (NaClO4) aqueous solution, barium perchlorate (Ba(ClO4)2) aqueous solution, and magnesium perchlorate (Mg(ClO4)2) aqueous solution. In particular, it is preferable to use sodium perchlorate (NaClO4) as the perchlorate aqueous solution.

[0009] The zinc secondary battery of the present invention has a battery container 101 in which a positive electrode material 106, a negative electrode material 103 containing zinc, a separator 109 having a conductive layer 110, and an electrolyte 108 that permeates the positive electrode material 106 and the negative electrode material 103 are arranged.

[0010] A positive terminal 107 is connected to the positive electrode material 106, a negative terminal 104 is connected to the negative electrode material 103, and a conductive terminal 111 is connected to the conductive layer 110. A dendrite generated from the negative electrode material 103 in contact with the conductive layer 110 is broken by applying a current between the negative terminal 104 and the conductive terminal 111.

[0011] The zinc secondary battery of the present invention can move or change at least one position among the separator 109, the positive electrode material 106, and the negative electrode material 103. By moving or changing the position, the generated dendrite 205 can be cut or destroyed.

Advantages of the Invention

[0012] The zinc secondary battery of the present invention has an extremely high theoretical capacity density and low raw material prices. Therefore, it can provide an inexpensive secondary battery. In addition, since zinc constituting the negative electrode can cut or destroy the dendrite 205, it exhibits the effect of long life.

Brief Description of the Drawings

[0013] [Figure 1] It is a configuration and explanatory diagram of the zinc secondary battery of the present invention. [Figure 2] It is a configuration and explanatory diagram of the zinc secondary battery of the present invention. [Figure 3] It is a configuration and explanatory diagram of the zinc secondary battery of the present invention. [Figure 4] It is an explanatory diagram of the relationship between the potential window and the NaOH concentration. [Figure 5] It is an explanatory diagram of the relationship between the oxygen evolution potential and the hydrogen evolution potential in 0.0001 mol / L NaOH. [Figure 6] It is an explanatory diagram of the relationship between the NaOH concentration and the oxygen evolution potential. [Figure 7] It is an explanatory diagram of the relationship between the NaOH concentration and the hydrogen evolution potential. [Figure 8] It is an explanatory diagram of the relationship between the NaOH concentration and the potential window. [Figure 9] It is an explanatory diagram of the relationship between Potential and current (density). [Figure 10] It is an explanatory diagram of the relationship between temperature and conductivity. [Figure 11] It is a configuration diagram and explanatory diagram of the zinc secondary battery of the present invention. [Figure 12] It is a configuration diagram and explanatory diagram of the zinc secondary battery of the present invention. [Figure 13]This is a diagram showing the configuration and explanatory diagram of the zinc secondary battery of the present invention. [Figure 14] This is a diagram showing the configuration and explanatory diagram of the zinc secondary battery of the present invention. [Figure 15] This is a diagram showing the configuration and explanatory diagram of the zinc secondary battery of the present invention. [Figure 16] This is a diagram showing the configuration and explanatory diagram of the zinc secondary battery of the present invention. [Figure 17] This is a diagram showing the configuration and explanatory diagram of the zinc secondary battery of the present invention. [Figure 18] This is a diagram showing the configuration and explanatory diagram of the zinc secondary battery of the present invention. [Figure 19] This is a diagram showing the configuration and explanatory diagram of the zinc secondary battery of the present invention. [Figure 20] This is a diagram showing the configuration and explanatory diagram of the zinc secondary battery unit of the present invention. [Figure 21] This is a diagram showing the configuration and explanatory diagram of the zinc secondary battery unit of the present invention. [Figure 22] This is a diagram showing the configuration and explanatory diagram of the zinc secondary battery unit of the present invention. [Figure 23] This is a configuration diagram and explanatory diagram of the drive control device of the present invention. [Modes for carrying out the invention]

[0014] Hereinafter, embodiments of the zinc secondary battery of the present invention will be described with reference to the drawings.

[0015] In the drawings illustrating embodiments for carrying out the invention, elements having the same function are denoted by the same reference numerals, and their descriptions may be omitted. Furthermore, the embodiments of the present invention described herein can be combined.

[0016] The zinc secondary battery of the present invention is not particularly limited as long as it contains zinc in the negative electrode and uses an alkaline hydroxide aqueous solution as the electrolyte. Therefore, it can be a nickel-zinc secondary battery, a silver-zinc secondary battery, a manganese-zinc secondary battery, a zinc-air secondary battery, or any other type of alkali-zinc secondary battery.

[0017] Figure 1 is a diagram illustrating the structure and operation of the zinc secondary battery of the present invention. The zinc secondary battery 500 has a positive electrode material 106, a negative electrode material 103, an electrolyte 108, and a separator 109 inside a battery container 101. The negative electrode material 103 contains zinc.

[0018] The zinc may be in any form, such as metal zinc, a zinc compound, or a zinc alloy, as long as it has electrochemical activity suitable for the negative electrode, and it may also be contained in the negative electrode material 103.

[0019] The positive electrode material 106 is selected according to the type of zinc secondary battery used. For example, in the case of a nickel-zinc secondary battery, nickel oxyhydroxide may be used; in the case of a silver-zinc secondary battery, silver oxide may be used; in the case of a manganese-zinc secondary battery, manganese dioxide may be used; and in the case of a zinc-air secondary battery, an air electrode that takes in oxygen from the air may be included. A negative electrode 102 is formed on or arranged on the negative electrode material 103, a negative terminal 104 is connected to the negative electrode 102, and the negative terminal 104 is led out to the outside of the battery container 101. A positive electrode 105 is formed on or arranged on the positive electrode material 106, a positive terminal 107 is connected to the positive electrode 105, and the positive terminal 107 is led out to the outside of the battery container 101.

[0020] Furthermore, the separator 109 has a conductive layer 110, and conductive terminals 111 are connected to the conductive layer 110 to supply or apply voltage or current. Although not shown in the figure, a conductive pattern is formed around the conductive layer 110. The conductive pattern is connected to the conductive terminals 111 and is configured to supply voltage or current to the conductive layer 110 without voltage drop.

[0021] The conductive layer 110 is preferably made of an alkali-resistant metal, such as titanium (alloy), iron (alloy), chromium, nickel (alloy), stainless steel, or Cu alloy casting.

[0022] As the conductive layer 110, materials other than metals can be used, such as graphite, carbon, and carbon quantum dots (CQDs). Other examples include artificial graphite, glassy carbon, amorphous carbon, carbon nanofoam, activated carbon, graphene, nanographene, graphene nanoribbons, fullerene, carbon black, carbon fiber, fibrous carbon, carbon nanotubes, carbon nanohorns, Vulcan, Ketjenblack, and acetylene black, and one or more of these can be used.

[0023] A metal oxide layer can also be used as the conductive layer 110. The metal oxide layer may be a single layer or may be configured or formed in multiple layers. Examples include tin, zinc, and chromium oxides. Other examples include one or more selected from indium oxide and germanium oxide.

[0024] The positive electrode material 106 and the negative electrode material 103 are immersed in or in contact with the electrolyte 108. The positive electrode material 106 and the electrolyte 108 do not necessarily need to be separate; the positive electrode material may be configured as a mixture of the positive electrode material 106 and the electrolyte. Similarly, the negative electrode material 103 and the electrolyte 108 do not necessarily need to be separate, and the negative electrode material may be configured as a mixture of the negative electrode and the electrolyte. The positive electrode material 106, the negative electrode material 103, and the electrolyte 108 can be configured according to the type of zinc secondary battery.

[0025] As shown in Figure 11, during charging, the Zn constituting the negative electrode generates dendrites (tree-like crystals), and these dendrites penetrate the separator 109, which prevents the positive electrode material 106 from electronically connecting to the negative electrode, and come into contact with the positive electrode material 106, causing a short circuit.

[0026] The positive electrode material 106 (NiOOH) and the negative electrode material 103 (Zn) are immersed in the electrolyte (NaOH aqueous solution) 108, and a separator 109 (a microporous membrane made of PP (polypropylene) or PE (polyethylene)) is interposed therebetween. The separator 109 electronically insulates the positive electrode material 106 and the negative electrode material 103 and plays a role of conducting OH - ions through the small holes 206. The battery reaction is shown by the following formula. (Positive electrode) 2NiOOH + 2H2O + 2e - → 2Ni(OH)2+ 2OH - ···(1-1) (Negative electrode) Zn + 4OH - → Zn(OH)4 2- + 2e - → ZnO + H2O + 2OH - + 2e - ···(1-2) Therefore, 2NiOOH + Zn + H2O → 2Ni(OH)2+ ZnO ····(1-3)

[0027] In the case of discharging, in the negative electrode material 103, Zn reacts with four OH - ions in the electrolyte 108 to become Zn(OH)4 2- ions. At this time, two electrons (e - ) are released to the external circuit. The generated Zn(OH)4 2- ions are in the electrolyte 108 including inside the small holes 206 of the separator 109, but on the electrode, OH - ions and H2O are expelled to become ZnO. In the positive electrode material 106, two electrons (e - ) coming through the external circuit react with NiOOH and H2O in the electrolyte 108 to become 2Ni(OH)2.

[0028] As shown in Figure 11, during charging, the reverse reaction described above occurs, and Zn is deposited on the negative electrode material 103. However, the current density is higher in the portion of the separator 109 facing the small pore 206, and the deposition rate is faster, forming the seeds of dendrites 205. The electric field strength at the tip of the dendrite 205 is high, causing Zn deposition to concentrate and the dendrite 205 to grow.

[0029] The tip of the dendrite 205 reaches the small pore 206 of the separator 109. Zn(OH)4 also enters the electrolyte 108 in the small pore 206 of the separator 109. 2- Ions are present. Even within the small pores 206, the dendrites 205 continue to grow, reaching the positive electrode material 106 and causing a short circuit inside the battery.

[0030] The separator 109 of the present invention has smaller pores 206 and distributes them uniformly across the entire surface of the separator 109. This reduces the bias in the current distribution and suppresses the generation of dendrite nuclei 205. As shown in Figure 11, the separator 109 is OH - It allows ions to pass through, but Zn(OH)4 2- It does not allow ions to pass through. As a result, even when the tip of dendrite 205 reaches separator 109, Zn(OH)4 remains inside the separator. 2- Since no ions are present, Zn is suppressed within separator 109. In one embodiment, the separator 109 of the battery of the present invention has a structure of three or more layers, consisting of an insulating layer 115a, a conductive layer 110, and an insulating layer 115b.

[0031] The insulating layer 115 of the separator 109 is an ion-conducting film. The ion-conducting film is stable in a strongly alkaline aqueous solution. The electron conduction resistance is 1 GΩ or more. Furthermore, in an alkaline aqueous solution, hydroxide ions (OH) - ) allows zincate ions (Zn(OH)4 2- ) does not pass through. hydroxide ions (OH - The conductivity is 0.01 S / cm. Hydroxide ions (OH) -The small pores 206 responsible for conduction are uniformly formed across the entire film surface. This allows for uniform dissolution and deposition of electrodes.

[0032] When the conductive layer 110 is made of metal, alkali-resistant metals such as titanium (alloy), iron (alloy), chromium, nickel (alloy), stainless steel, or Cu alloy castings are used or selected. Alternatively, tin, zinc, etc., may be used or selected. Furthermore, the conductive layer 110 is not limited to foil, plate, or thin film form, but may also be in the form of a mesh, foamed copper, or perforated material.

[0033] For the conductive layer 110, materials other than metals can be used, such as graphite, carbon, or carbon quantum dots (CQDs). Carbon quantum dots (CQDs) are nanoparticles with a size of less than 10 nm.

[0034] Examples of other materials include artificial graphite, glassy carbon, amorphous carbon, graphitized carbon, carbon nanofoam, activated carbon, graphene, nanographene, graphene nanoribbons, fullerene, carbon black, carbon fiber, fibrous carbon, carbon nanotubes, carbon nanohorns, Vulcan, Ketjenblack, and acetylene black, and one or more of these can be used.

[0035] When iron oxide (Fe2O3) is used as the conductive layer 110, it is preferable to disperse CQDs in the iron oxide. The presence of CQDs in the Fe2O3 film can increase the conductivity of the Fe2O3 film.

[0036] Iron oxide (Fe2O3) has disadvantages such as low chemical stability and poor conductivity. Adding, mixing, or incorporating phosphorus (P) into iron oxide (Fe2O3) stabilizes it.

[0037] The conductive layer 110 may be formed or constructed by electrodeposition, plating, vapor deposition, or screen printing. Alternatively, conductive materials such as metals may be sputtered to deposit conductive carbon material, metal oxides, phosphorus, etc.

[0038] The conductive layer 110 is formed as a thin film, and by crystallization or sintering, small pores are formed in the thin film, into which the electrolyte penetrates 206. An insulating layer 115, acting as a separator, is formed or arranged on the front and rear surfaces of the conductive layer 110.

[0039] The separator 109 used in the battery of the present invention has a multilayer structure including an insulating layer and a conductive layer. The multilayer structure only needs to include at least one insulating layer and one conductive layer.

[0040] The separator 109 of the present invention is preferably composed of a three-layer structure of insulating layer 115a / conductive layer 110 / insulating layer 115b. The separator 109 of the present invention is said to include a three-layer structure of insulating layer 115a / conductive layer 110 / insulating layer 115b, but it is sufficient that it includes at least these three layers. For example, the separator 109 of the present invention may have a four-layer structure of conductive layer / insulating layer / conductive layer / insulating layer.

[0041] The conductive layer 110 of the separator 109 only needs to have a conductivity greater than that of the electrolyte 108. Since the conductive layer 110 is formed or constitutes the entire surface of the separator 109, the sheet resistance can be kept low even if it is made of a material with low conductivity. The sheet resistance of the conductive layer 110 is preferably 1000 Ω / sq or less, and more preferably 100 Ω / sq or less. Figure 9 is an explanatory diagram of the cyclic voltammogram (CV) of a saturated perchlorate aqueous solution. An Ag / AgCl electrode was used as the reference electrode. In the CV measurement shown in Figure 9, no current flows in the flat areas. This means that the water decomposition reaction is not occurring. The flat areas represent the potential window.

[0042] The potential window for saturated sodium perchlorate solution and saturated lithium perchlorate solution is 3.2V, and it can be seen that saturated magnesium perchlorate, saturated perchlorate solution, and saturated barium perchlorate solution also have a wide potential window (approximately 3V).

[0043] This means that saturated lithium perchlorate (LiClO4) aqueous solution, saturated sodium perchlorate (NaClO4) aqueous solution, saturated barium perchlorate (Ba(ClO4)2) aqueous solution, and saturated magnesium perchlorate (Mg(ClO4)2) aqueous solution can be used as electrolytes in secondary batteries.

[0044] As illustrated in Figure 9, saturated aqueous solutions of perchlorate salts, in particular, have a wide potential window. Using these aqueous solutions as electrolytes makes it possible to manipulate high applied voltages. Figure 10 is an explanatory diagram illustrating the conductivity of saturated lithium perchlorate aqueous solution and its temperature dependence. The conductivity of a saturated lithium perchlorate solution is greater than that of a saturated sodium perchlorate solution. In both cases, conductivity increases with increasing temperature.

[0045] In Figure 10, the horizontal axis of the graph represents temperature, and the vertical axis represents conductivity in millisiemens per centimeter (mS / cm). The conductivity of lithium perchlorate (LiClO4) aqueous solution is higher than that of saturated NaClO4 aqueous solution.

[0046] However, the temperature dependence of the conductivity of an aqueous lithium perchlorate (LiClO4) solution is greater than that of an aqueous saturated NaClO4 solution. Furthermore, as shown in Figure 9, the potential window of lithium perchlorate (LiClO4) is narrower than that of sodium perchlorate (NaClO4). Therefore, sodium perchlorate (NaClO4) is preferred.

[0047] While this invention primarily describes sodium perchlorate (NaClO4), it is not limited to this. As illustrated in Figure 9, aqueous lithium perchlorate (LiClO4), aqueous barium perchlorate (Ba(ClO4)2), and magnesium perchlorate (Mg(ClO4)2) may also be used. Figure 4 is an explanatory diagram illustrating the relationship between NaOH concentration (mol / L) and potential window (V) in the zinc secondary battery of the present invention.

[0048] The working electrode is GC (glassy carbon), the counter electrode is Pt, and the reference electrode is Hg / HgO / NaOH. The electrolyte is NaClO4, and the NaOH is varied. The measurement method is Linear Sweep Voltammetry (LSV), and the sweep rate is 5mV / sec.

[0049] As described above, in one embodiment, a perchlorate aqueous solution is added to an alkaline electrolyte solution NaOH. Note that this is not limited to sodium perchlorate (NaClO4), but other perchlorate aqueous solutions include lithium perchlorate (LiClO4) aqueous solution, sodium perchlorate (NaClO4) aqueous solution, barium perchlorate (Ba(ClO4)2) aqueous solution, and magnesium perchlorate (Mg(ClO4)2) aqueous solution.

[0050] Figure 4 graphs the potential window (V) as the concentration of sodium perchlorate (NaClO4) is varied, with the NaOH concentration (mol / L) on the x-axis. pH is shown for supplementary information for the NaOH concentration (mol / L).

[0051] The diagram shows sodium perchlorate (NaClO4) concentrations of 6 mol / L, 7 mol / L, 8 mol / L, and 9 mol / L. As the mol / L concentration increases, the potential window (V) rises, but it saturates at 9 mol / L. Furthermore, the difference in the potential window between 8 mol / L and 9 mol / L is small. Therefore, it is preferable to use a concentration of 8 mol / L or higher.

[0052] Figure 5 graphs the oxygen and hydrogen evolution potentials when NaOH is 0.0001 mol / L. The potential window is ±0.05 mA. The graphs for NaClO4 = 8 mol / L and NaClO4 = 1 mol / L are shown. Note that the graphs for NaClO4 = 8 mol / L and NaClO4 = 9 mol / L are almost identical.

[0053] As illustrated in Figures 4 and 6, the potential window decreases as the mol / L concentration of NaClO4 decreases. The graph in Figure 5 also shows that it is preferable to use or adopt saturated sodium perchlorate (NaClO4) in zinc secondary batteries, with a concentration of 8 mol / L or higher. Since the potential window widened in the range of 0.0001 to 0.01 mol / L for NaOH concentrations, it can be concluded that NaOH concentrations within this range are appropriate for the electrolyte.

[0054] Figure 6 is a graph showing the oxygen evolution potential in response to changes in NaOH concentration. Similar to the potential window, the oxygen evolution potential increased in the range of NaOH concentration from 0.0001 to 0.01 mol / L. In other words, it can be seen that oxygen evolution was suppressed within this concentration range. Figure 7 is a graph showing the hydrogen evolution potential in response to changes in NaOH concentration. No significant changes in the hydrogen evolution potential were observed with respect to changes in NaOH concentration.

[0055] Figure 8 is a graph showing the relationship between the potential window (V) and conductivity (ms / cm). Similar to the potential window, conductivity is high in the range of NaOH concentration from 0.0001 to 0.01 mol / L, so a concentration range of 0.0001 to 0.01 mol / L is appropriate for NaOH.

[0056] The zinc secondary battery of the present invention uses NaClO4 as the electrolyte, with NaOH added. In one embodiment, a perchlorate aqueous solution is added to the alkaline electrolyte NaOH. Examples of perchlorate aqueous solutions include lithium perchlorate (LiClO4) aqueous solution, sodium perchlorate (NaClO4) aqueous solution, barium perchlorate (Ba(ClO4)2) aqueous solution, and magnesium perchlorate (Mg(ClO4)2) aqueous solution. In particular, it is preferable to use sodium perchlorate (NaClO4) as the perchlorate aqueous solution.

[0057] As the mol / L concentration of sodium perchlorate (NaClO4) increases from 6 mol / L to 7 mol / L, 8 mol / L, and 9 mol / L, the potential window (V) increases, but it saturates at 9 mol / L. Furthermore, the difference in the potential window between 8 mol / L and 9 mol / L is small. Therefore, it is preferable to use a sodium perchlorate (NaClO4) concentration of 8 mol / L or higher.

[0058] The potential window widens in the range of 0.0001 to 0.01 mol / L for NaOH concentrations, indicating that NaOH concentrations within this range are appropriate for the electrolyte. The oxygen evolution potential increases in the range of 0.0001 to 0.01 mol / L for NaOH concentrations, indicating that oxygen evolution is suppressed within this concentration range. No significant change in hydrogen evolution potential is observed with changes in NaOH concentration.

[0059] Figure 2 is a diagram illustrating the configuration and operation of the coin-type zinc secondary battery of the present invention. While Figure 2 illustrates a coin-type secondary battery, the technical concept of the present invention is not limited to this. For example, as shown in Figure 3, it may also be cylindrical or other shapes. Other examples include film-shaped and box-shaped batteries.

[0060] As shown in Figure 2, the separator 109 of the zinc secondary battery of the present invention is permeated and impregnated with electrolyte 108a and electrolyte 108b. A positive electrode 105 is formed or arranged on the positive electrode material 106. The positive electrode 105 is configured or arranged to be electrically connected to the positive electrode case 202 (positive terminal 107). A negative electrode 102 is formed or arranged on the negative electrode material 103. The negative electrode 102 is configured or arranged to be electrically connected to the negative electrode case 201 (negative terminal 104).

[0061] The negative electrode case 201 and the positive electrode case 202 are insulated by a gasket 203. The negative electrode case 201, the positive electrode case 202, and the gasket 203 constitute a coin-type battery, and the electrolyte 108 is sealed inside. It goes without saying that the zinc secondary battery of the present invention may be cylindrical or otherwise shaped, as shown in Figure 3.

[0062] As shown in Figure 3, the zinc secondary battery of the present invention comprises a battery container 101 containing a positive electrode material 106, a negative electrode material 103, and a separator 109. An insulating film 204 is also formed or arranged as needed. An electrolyte 108 is filled between the separator 109, the positive electrode material 106, and the negative electrode material 103.

[0063] A positive electrode (not shown) is formed or arranged on the positive electrode material 106. The positive electrode is configured or arranged to be electrically connected to the positive electrode case (positive terminal 107). A negative electrode (not shown) is formed or arranged on the negative electrode material 103. The negative electrode is configured or arranged to be electrically connected to the negative electrode case (negative terminal 104).

[0064] In zinc secondary batteries, as shown in Figure 11, there is a problem in that during charging, the Zn constituting the negative electrode generates dendrites 205 (tree-like crystals), which break through the separator 109 and electrically short-circuit the positive electrode material 106 and the negative electrode.

[0065] In one embodiment, the separator 109 of the zinc secondary battery of the present invention has a structure of three or more layers: an insulating layer 115a, a conductive layer 110, and an insulating layer 115b. The conductive layer 110 is configured to allow current or voltage to be applied or supplied via conductive terminals 111. The current or voltage is supplied between at least one of the following: the conductive layer 110 and the negative electrode 102, the conductive layer 110 and the positive electrode 105, and the negative electrode 102 and the positive electrode 105. Conductive terminals 111 are connected to or arranged on the conductive layer 110.

[0066] Figure 12 is a schematic diagram illustrating the state in which the dendrite 205 has grown and is in contact (connected) with the conductive layer 110 at the position indicated by the dotted circle. A positive electrode 105 is formed on or arranged on the positive electrode material 106, a positive terminal 107 is connected to the positive electrode 105, and the positive terminal 107 is led out to the outside of the battery container 101.

[0067] Furthermore, the separator 109 has a conductive layer 110, and conductive terminals 111 are connected to the conductive layer 110 to supply or apply voltage or current. Although not shown in the figure, a conductive pattern is formed around the conductive layer 110. The conductive pattern is connected to the conductive terminals 111 and is configured to supply voltage or current to the conductive layer 110 without voltage drop.

[0068] In Figure 12, when the switch circuit 114 is turned on (closed), the (variable) voltage (current) circuit 112 is connected between the conductive terminal 111 and the negative terminal 104. The (variable) voltage (current) circuit 112 can apply or supply at least one of voltage and current between the conductive terminal 111 and the negative terminal 104. Furthermore, the magnitude of the supplied or applied current and voltage can be changed and set.

[0069] The (variable) voltage (current) circuit 112 can vary the polarity and magnitude of the current. It can also vary the polarity and magnitude of the voltage. Furthermore, it can monitor the presence and magnitude of the current flowing and control the on (closed) and off (open) states of the switch circuit 114.

[0070] As the dendrite 205 grows and comes into contact with the conductive layer 110, a current path is generated between the negative electrode 102 and the conductive layer 110. When a current or voltage is applied by the (variable) voltage (current) circuit 112, current flows to the dendrite 205 at the location indicated by the dotted circle in Figure 12, generating heat and causing the dendrite 205 to break. Therefore, the growth of the dendrite 205 is stopped, and a short circuit between the negative electrode 102 and the positive electrode 105 can be prevented or suppressed. Figure 12 shows a (variable) voltage (current) circuit 112, which is configured and used to cut the dendrite 205, but the present invention is not limited to this.

[0071] Figure 13 shows an embodiment in which resistance is measured and monitored between at least one of the following: between the conductive layer 110 and the negative electrode 102, between the conductive layer 110 and the positive electrode 105, and between the negative electrode 102 and the positive electrode 105. In this embodiment, pulsed current or voltage is supplied between at least one of the following: between the conductive layer 110 and the negative electrode 102, between the conductive layer 110 and the positive electrode 105, and between the negative electrode 102 and the positive electrode 105.

[0072] The pulse generator 117 can vary the polarity direction and magnitude of the pulse current. It can also vary the polarity direction and magnitude of the pulse voltage. Furthermore, it can monitor the presence and magnitude of the flowing current and control the on (closed) and off (open) states of the switch circuit 114, as well as the switching of terminals a and b of the switch circuit 114. It goes without saying that the pulse generator 117 can be replaced with the (variable) voltage (current) circuit 112.

[0073] By connecting the switch circuit 114 to terminal a, the pulse generator 117 is connected between the conductive terminal 111 and the negative terminal 104. By connecting the switch circuit 114 to terminal b, the resistance meter 116 is connected between the conductive terminal 111 and the negative terminal 104.

[0074] The resistance meter 116 is a device for measuring or monitoring the resistance between the conductive terminal 111 and the negative terminal 104. However, the resistance meter is not limited to 116; the resistance can also be measured or monitored indirectly by applying a predetermined current and measuring the voltage drop.

[0075] When the dendrites 205 grow and come into contact with the conductive layer 110, a current path is generated between the negative electrode 102 and the conductive layer 110. Alternatively, the resistance value decreases. The generation of the current path and the state of its generation can be determined by measuring the resistance value with the resistance meter 116. Furthermore, the state of dendrite growth can be understood by periodically monitoring the resistance value at predetermined intervals or continuously.

[0076] The switch circuit 114 is connected to terminal b, and when the resistance value measured by the resistance meter 116 falls below a predetermined value, it is determined that a dendrite 205 has formed. The change in resistance value and the rate of change are also observed and monitored. If the rate of change exceeds a predetermined value, it is determined that a dendrite 205 has formed or will form. The resistance value is approximately M (mega) ohms (Ω) or less.

[0077] If a dendrite 205 is generated or is deemed likely to be generated, the switch circuit 114 is switched to terminal a, and a pulse generator 117 (voltage / current source 112) is connected between the conductive terminal 111 and the negative terminal 104.

[0078] In the embodiments of the present invention, a pulse generator 117 (voltage / current source 112) is connected between the conductive terminal 111 and the negative terminal 104, and the resistance value between the conductive terminal 111 and the negative terminal 104 is measured or monitored. However, the invention is not limited to this. Alternatively, a pulse generator 117 (voltage / current source 112) may be connected between the conductive terminal 111 and the positive terminal 107, and the resistance value between the conductive terminal 111 and the positive terminal 107 may be measured or monitored. Furthermore, a pulse generator 117 (voltage / current source 112) may be connected between the negative terminal 104 and the positive terminal 107, and the resistance value between the negative terminal 104 and the positive terminal 107 may be measured or monitored.

[0079] The pulses generated by the pulse generator 117 are not limited to a rectangular shape. A pulse is a signal with a relatively high peak value. It may be a sine wave, multiple pulses, a triangular wave, etc.

[0080] By applying a pulsed signal waveform with the pulse generator 117, the high-resistance dendrites 205, or the areas where the dendrites 205 and the conductive layer 110 are in contact, heat up and are cut. This cutting of the dendrites 205 destroys them and stops their growth.

[0081] Preferably, the pulse height, magnitude, current or voltage, and application period of the pulse applied by the pulse generator 117 are set or changed based on the resistance value measured or monitored by the resistance meter 116. For example, if the resistance value is relatively high, the pulse height value etc. are set lower. If the resistance value is high, the pulse height value etc. are set higher, assuming that the contact of the dendrite 205 is strong.

[0082] When current or voltage is applied using the (variable) voltage (current) circuit 112 or pulse generator 117, current flows to the dendrite 205 at the dotted circle in Figures 12 and 13, generating heat and causing the dendrite 205 to break. Therefore, the growth of the dendrite 205 is stopped, preventing or suppressing a short circuit between the negative electrode 102 and the positive electrode 105. The embodiments shown in Figures 12 and 13 involved a structure and method in which an electric current or the like was applied to the dendrite 205, causing it to be destroyed or cut by heating and melting. Figure 14 shows an embodiment of a configuration and method for moving the separator 109 and mechanically destroying the dendrite 205.

[0083] The separator 109 has small holes 206, and the electrolyte 108 enters into the small holes 206, OH - Ions are allowed to move. As the dendrite 205 grows, it either enters the pore 206 or breaks through the separator 109 and reaches the positive electrode 105. When the dendrite 205 reaches the positive electrode 105, a short circuit occurs between the positive electrode 105 and the negative electrode 102.

[0084] Figure 14 is a configuration diagram and explanatory diagram of an embodiment of the present invention that prevents short circuits using dendrites 205. As shown in Figure 14, the separator 109 is configured to move or vibrate. The dendrites 205 grow in the small holes 206 of the separator 109.

[0085] As shown in Figure 14(a), dendrite 205a penetrates and grows in the small pore 206a. Dendrite 205b penetrates and grows in the small pore 206b. When dendrite 205a or dendrite 205b comes into contact with the positive electrode 105, the positive electrode 105 and the negative electrode 102 are short-circuited.

[0086] As shown in Figure 14(b), the separator 109 moves in the direction of arrow A. By moving in the direction of arrow A, the dendrites 205a that have entered the small hole 206a are cut or destroyed. Also, the dendrites 205b that have entered the small hole 206b are cut or destroyed. By cutting or otherwise destroying the dendrites 205, the growth of the dendrites 205 can be stopped. In addition, short circuits between electrodes caused by the dendrites 205 can be prevented.

[0087] The separator 109 can be moved in direction A or direction B. Furthermore, vibration can be applied to the separator 109. The vibration is generated and applied using ultrasonic waves, such as a piezoelectric element. By moving the separator 109 and applying vibration, the growth of the dendrites 205 can be stopped, and short circuits between electrodes caused by the dendrites 205 can be prevented.

[0088] Figure 15 is an explanatory diagram of the structure and method for causing the separator 109 to move and vibrate. As shown in Figure 15, an elastic body 207 is formed or arranged in the battery container 101. The elastic body 207 is an object that has elasticity, and examples include rubber, springs, sponges, and sea sponges. The elastic body 207 may also be a viscous body.

[0089] In the embodiments shown in Figures 14 and 15, it is explained that when the separator 109 is pressed, the elastic body 207 is distorted or deformed, and the position of the small hole 206 of the separator 109 moves, but the invention is not limited to this.

[0090] For example, the separator 109 may be configured such that when it is deformed by compression, expansion, etc., the position of the small hole 206 in the separator 109 moves or deforms, thereby destroying or cutting the dendrite 205. In this embodiment, the elastic body 207 can be omitted.

[0091] In the embodiment shown in Figure 15, an elastic body 207 is arranged or formed in the battery container 101, and a separator 109 is placed between the elastic body 207 and the pressure cap 208. The pressure cap 208 is a button-shaped object made of a rubber material such as butyl rubber or silicone rubber, or a resin material such as silicone or polyester. The pressure cap 208 can be deformed by pressing it.

[0092] The pressure cap 208 is attached to the ring-shaped pressure part 209. By pressing the pressure cap 208, the separator 109 is pressed. The pressure on the separator 109 deforms the elastic body 207, and the position of the separator 109 changes. As shown in Figure 14, the dendrite 205 can be destroyed or cut by the change in the position of the separator 109. The position of the separator 109 and the position of the conductive layer 110 may also be changed by pulling the pressure cap 208.

[0093] In the embodiment shown in Figure 15, the separator 109 has a conductive layer 110, and conductive terminals 111 are connected to the conductive layer 110. As shown in Figures 12 and 13, a voltage or current can be applied to the dendrite 205 by a voltage / current source 112 and a pulse generator 117, thereby cutting or destroying the dendrite 205.

[0094] Figure 15 is a diagram illustrating the structure and operation of the zinc secondary battery of the present invention. The zinc secondary battery 500 has a positive electrode material 106, a negative electrode material 103, an electrolyte 108, and a separator 109 inside a battery container 101. The negative electrode material 103 contains zinc.

[0095] A negative electrode 102 is formed or arranged on the negative electrode material 103, a negative terminal 104 is connected to the negative electrode 102, and the negative terminal 104 is led out to the outside of the battery container 101. A positive electrode 105 is formed or arranged on the positive electrode material 106, a positive terminal 107 is connected to the positive electrode 105, and the positive terminal 107 is led out to the outside of the battery container 101. In addition, a conductive terminal 111 is connected to the conductive layer 110.

[0096] The positive electrode material 106 and the negative electrode material 103 are immersed in or in contact with the electrolyte 108. The positive electrode material 106 and the electrolyte 108 do not necessarily have to be separated, and the positive electrode material may be configured as a mixture of the positive electrode material 106 and the electrolyte. Similarly, the negative electrode material 103 and the electrolyte 108 do not necessarily have to be separated, and the negative electrode material may be configured as a mixture of the negative electrode and the electrolyte.

[0097] The positive electrode material 106, negative electrode material 103, and electrolyte 108 should be selected and configured according to the type of zinc (secondary) battery 500. The spacing between the positive electrode material 106 and the negative electrode material 103 is configured to be variable. By shortening the distance between the positive electrode material 106 and the negative electrode material 103, the resistance between the electrodes can be reduced. The spacing between the positive electrode material 106 and the negative electrode material 103 can be set and adjusted by changing the positions of the positive terminal 107 and the negative terminal 104.

[0098] As shown in Figure 16(a), the elastic body 207 is not deformed when the pressure cap 208 is not pressed down. As shown in Figure 16(b), the elastic body 207 deforms when the pressure cap 208 is pressed down. When the elastic body 207 deforms, the position of the separator 109 in Figure 16(b) changes relative to the position of the separator 109 in Figure 16(a).

[0099] The change in the position of the separator 109 causes the position of the small hole 206 to shift, allowing the dendrite 205 to be cut or destroyed, as shown in Figure 14. By cutting or otherwise destroying the dendrite 205, the growth of the dendrite 205 can be stopped. In addition, short circuits between electrodes caused by the dendrite 205 can be prevented.

[0100] Figure 16(b) shows the state in which the pressure cap 208 is pressed, while Figure 16(a) shows the state in which the pressure cap 208 is not pressed. The state shown in Figure 16(a) and Figure 16(b) can be switched by whether or not the pressure cap 208 is pressed.

[0101] Figure 17 illustrates an embodiment in which the press-button cap 208 is pressed by attaching the zinc secondary battery 500 of the present invention to the battery box 301, and a method is used to release the press-button cap 208 from its pressed state by removing the zinc secondary battery 500 from the battery box 301.

[0102] The battery box 301 is fitted with a spring fitting 302 and a connecting fitting 303. As shown in Figure 17(a), when the zinc secondary battery 500 is not installed in the battery box 301, the press cap 208 of the zinc secondary battery 500 is not pressed. Therefore, the separator 109 is in an unpressed state.

[0103] As shown in Figure 17(b), when the zinc secondary battery 500 is installed in the battery box 301, the zinc secondary battery 500 is sandwiched between the spring fitting 302 and the connecting fitting 303. The pressure cap 208 of the zinc secondary battery 500 is pressed by the spring fitting 302. Therefore, the separator 109 is in a pressed state.

[0104] As shown in Figure 17(b), by switching between a state in which the zinc secondary battery 500 is installed in the battery box 301 and a state in which the zinc secondary battery 500 is not installed in the battery box 301, as shown in Figure 17(a), the position of the separator 109 can be changed, and as shown in Figure 14, the dendrite 205 can be cut or destroyed.

[0105] In the embodiments of the present invention, the position of the separator 109 is described as being changed. Alternatively, vibrations such as ultrasonic vibrations may be applied to the separator 109 to cause it to vibrate, thereby changing the position of the separator 109, the small hole 206, etc., and cutting or destroying the dendrite 205.

[0106] The embodiment shown in Figure 17 involved a configuration and method for preventing or suppressing short circuits caused by dendrites 205 by attaching and removing a zinc secondary battery 500 from a battery box 301. The present invention is not limited thereto. Figure 18 is an explanatory diagram of a configuration and method for achieving a change in the position of the separator 109 of the zinc secondary battery 500 in synchronization with the rotation of the rotating body 304.

[0107] The rotating body 304 has a protrusion 305 formed on or positioned on it. The rotating body 304 rotates around the center C as its axis. The rotational motion is not limited to continuous motion. As the rotating body 304 rotates, the position of the protrusion 305 moves in the direction of the arrow.

[0108] As shown in Figure 18(a), when the protrusion 305 is positioned at the location of the pressure cap 208, the pressure cap 208 is pressed, causing the position of the separator 109 to change. Alternatively, vibrations such as ultrasonic waves are applied to the separator 109. By applying or supplying vibrations, the dendrite 205 can be cut or destroyed.

[0109] As shown in Figure 18(b), when the protrusion 305 is not in contact with the pressure cap 208, the pressure cap 208 is not pressed, and the position of the separator 109 does not change. Alternatively, no vibration is applied to the separator 109.

[0110] As shown in Figure 18, the rotating body 304 rotates, causing the position of the protrusion 305 to rotate, which in turn causes the pressing cap 208 to be pressed or not pressed, and vibration is applied to the separator 109. By vibrating the separator 109, the positions of the separator 109, the small hole 206, etc. are changed, cutting or destroying the dendrite 205. By cutting or destroying the dendrite 205, the growth of the dendrite 205 can be stopped. In addition, short circuits between electrodes caused by the dendrite 205 can be prevented.

[0111] In the above embodiments, the dendrites 205 were destroyed by changing the position of the separator 109 or by vibrating the separator 109, but the present invention is not limited thereto.

[0112] Figure 19 shows an embodiment in which the position of the separator 109 is fixed, and the position of at least one of the positive electrode material 106 and the negative electrode material 103 can be changed, modified, or subjected to vibration.

[0113] The zinc secondary battery 500 has a positive electrode material 106, a negative electrode material 103, an electrolyte 108, a separator 109, etc., inside the battery container 101. The negative electrode material 103 is made of zinc, a zinc-containing metal, or a zinc alloy.

[0114] A negative electrode 102 is formed or arranged on the negative electrode material 103, a negative terminal 104 is connected to the negative electrode 102, and the negative terminal 104 is led out to the outside of the battery container 101. A positive electrode 105 is formed or arranged on the positive electrode material 106, a positive terminal 107 is connected to the positive electrode 105, and the positive terminal 107 is led out to the outside of the battery container 101. In addition, a conductive terminal 111 is connected to the conductive layer 110.

[0115] The positive electrode material 106 and the negative electrode material 103 are immersed in or in contact with an alkaline electrolyte 108. The positive electrode material 106 and the electrolyte 108 do not necessarily have to be separate, and the positive electrode material may be configured as a mixture of the positive electrode material 106 and the electrolyte, permeated, or immersed together. Similarly, the negative electrode material 103 and the electrolyte 108 do not necessarily have to be separate, and the negative electrode material may be configured as a mixture of the negative electrode and the electrolyte, permeated, or immersed together.

[0116] The positive electrode material 106, the negative electrode material 103, and the electrolyte 108 can be configured according to the type of zinc secondary battery. The distance between the positive electrode material 106 and the negative electrode material 103 is configured to be variable. By shortening the distance between the positive electrode material 106 and the negative electrode material 103, the output current of the battery can be increased.

[0117] The negative electrode material 103 is placed on the elastic body 207a, and the positive electrode material 106 is placed on the elastic body 207b. A negative electrode 102 is formed on or placed on the negative electrode material 103. A positive electrode 105 is formed on or placed on the positive electrode material 106. A negative terminal 104 is connected to the negative electrode 102, and a positive terminal 107 is connected to the positive electrode 105.

[0118] A pressure cap 208a is positioned on the negative electrode material 103 side, and the pressure cap 208a is attached to the pressure portion 209a. A pressure cap 208b is positioned on the positive electrode material 106 side, and the pressure cap 208b is attached to the pressure portion 209b.

[0119] In the embodiments of the present invention, the structure is described as a pressure cap 208, but it is not limited to a cap shape. Any configuration or method is acceptable as long as the component such as the pressure cap 208 can apply, supply, or generate mechanical pressure to the negative electrode material 103, positive electrode material 106, and separator 109. When the pressure cap 208 is not pressed down, the elastic body 207 is not deformed. When the pressure cap 208 is pressed down, the elastic body 207 deforms.

[0120] When the elastic body 207 is deformed, the position of the positive electrode material 106 or the negative electrode material 103 fluctuates or moves. By causing the position of the positive electrode material 106 or the negative electrode material 103 to fluctuate or move, the dendrites 205 can be cut or destroyed. Alternatively, the generation of dendrites 205 can be suppressed. Alternatively, the growth of dendrites 205 can be stopped by cutting or otherwise destroying them. Furthermore, short circuits between electrodes caused by dendrites 205 can be prevented.

[0121] Furthermore, by vibrating the positive electrode material 106 or the negative electrode material 103, the dendrites 205 can be cut or otherwise damaged, thereby stopping their growth. This also prevents short circuits between electrodes caused by the dendrites 205.

[0122] Figures 20, 21, and 22 are configuration diagrams and explanatory diagrams of a battery unit having multiple zinc secondary batteries according to the present invention. In Figures 20, 21, and 22, the zinc secondary battery 500 is shown as battery B. The capacity of the zinc secondary batteries 500 is not limited to being the same. The capacities of the zinc (secondary) batteries 500 may be different.

[0123] Figure 20 is an explanatory diagram of the battery unit of the present invention. As shown in Figure 20, the battery unit of the present invention has a battery unit 307a and a battery unit 307b configured or arranged within a housing 509.

[0124] As one embodiment shown in Figure 20, battery unit 307a has two batteries B. Battery unit 307b has twelve batteries B. The batteries B are connected to the negative terminal 104 and the positive terminal 107 by connecting wires 306a, 306b, and 306c.

[0125] Battery B of battery unit 307a is connected to the positive terminal 107b of housing 509 and to the negative terminal 104 of housing 509. Battery B of battery unit 307b is connected to the positive terminal 107a of housing 509 and to the negative terminal 104 of housing 509.

[0126] In the embodiment shown in Figure 20, battery unit 307a and battery unit 307b share a common negative terminal 104. The positive terminal 107b of battery unit 307a and the positive terminal 107a of battery unit 307b are independent. Battery unit 307a has 2 batteries B, and battery unit 307b has 12 batteries B, so the capacity of battery unit 307b is greater than the capacity of battery unit 307a.

[0127] In the embodiment shown in Figure 20, the negative terminal 104 of battery unit 307a and the negative terminal 104 of battery unit 307b are made common, the positive terminal of battery unit 307a is connected to the positive terminal 107b, and the positive terminal of battery unit 307b is connected to the positive terminal 107a. This allows for the configuration of multiple battery units 307 with the same voltage value but different power capacities. Battery units of different capacities can be used in a single housing 509.

[0128] Figure 21 is an explanatory diagram of the battery unit of the present invention in another embodiment. As shown in Figure 21, the battery unit of the present invention has a battery unit 307a and a battery unit 307b configured or arranged within a housing 509.

[0129] As one embodiment shown in Figure 21, battery unit 307a has four batteries B. Battery unit 307b has twelve batteries B. The batteries B are connected to the negative terminal 104 or the positive terminal 107 by connecting wires 306a, 306b, and 306c.

[0130] Two batteries B in battery unit 307a are connected to the positive terminal 107b, and the other two batteries B in battery unit 307a are connected to the positive terminal 107c. All four batteries B in battery unit 307a are connected to the common negative terminal 104b. The batteries B in battery unit 307b are connected to the positive terminal 107a and the negative terminal 104a.

[0131] In the embodiment shown in Figure 21, battery units 307a and 307b are separated into negative terminals 104a and 104b. The positive terminal 107a of battery unit 307a and the positive terminals 107b and 107c of battery unit 307b are kept separate. Battery unit 307a has 4 batteries B, and battery unit 307b has 12 batteries B, so the capacity of battery unit 307b is greater than the capacity of battery unit 307a.

[0132] In the embodiment shown in Figure 21, by separating the negative terminal 104b of battery unit 307a from the negative terminal 104a of battery unit 307b, connecting the positive terminal of battery unit 307b to the positive terminal 107a, and connecting the positive terminal of battery unit 307a to either the positive terminal 107b or the positive terminal 107c, multiple battery units 307 with the same voltage value but different power capacities can be configured. Furthermore, power supply units 307a and 307b can be used as batteries with independent potentials.

[0133] The embodiment shown in Figure 22 has a battery device configured with a switch circuit 505 in a housing 509. Turning the switch circuit 505 on (closed) connects battery B to the positive terminal 107. Turning the switch circuit 505 off (open) disconnects battery B from the positive terminal 107. The on / off state of the switch circuit 505 is controlled by the drive control circuit 506 based on the magnitude of the current output from the positive terminal 107. The magnitude of the current is measured and monitored by a current sensor 508, as shown in Figure 23.

[0134] Figure 22(a) shows an embodiment in which the battery unit 307 has six batteries. It goes without saying that the number of batteries is not limited to six; it can be six or fewer, or six or more. Switch circuits 505 (switch circuits S1 to S6) are arranged for batteries 500 (batteries B1 to B6). In Figure 22(a), switch circuit S6 is open, and the other switch circuits are closed. The more switch circuits 505 that are turned on, the larger the current value that can be output from the positive terminal 107 can be.

[0135] The negative electrodes of the six batteries 500 are connected to the negative terminal 104, which is connected to ground "GND". The positive electrodes of the six batteries 500 are connected to the positive terminals 107a and 107b, which output a (predetermined) voltage "V1". The positive terminals 107a and 107b are located at both ends of the battery unit 307.

[0136] If there is a difference between the voltage "V1" at positive terminal 107a and the voltage "V1" at positive terminal 107b, the drive control circuit 506 controls the position and number of switches 505 to be turned on, so that the voltage "V1" at positive terminal 107a and the voltage "V1" at positive terminal 107b become the same.

[0137] Figure 22(b) shows an embodiment in which battery B is arranged in two series stages, with six sets of these two-stage battery configurations. Note that this is not limited to two stages; three or more stages are also possible. Furthermore, it goes without saying that batteries can be connected in parallel or series.

[0138] Figure 22(b) shows one embodiment in which there are six sets of two-stage series connections. A switch circuit 505 (switch circuits S1 to S6) is arranged for the batteries 500 (batteries B1a to B6a, batteries B1b to B6b).

[0139] In Figure 22(b), switch circuits S4 and S6 are open, while the other switch circuits are closed. The more switch circuits 505 that are turned on, the larger the current that can be output from the positive terminal 107.

[0140] The negative electrodes of the four battery sets located on the left side of Figure 22(b) are connected to negative terminal 104a, which is connected to ground 1 "GND1". The negative electrodes of the two battery sets located on the right side of the figure are connected to negative terminal 104b, which is connected to ground 2 "GND2".

[0141] In Figure 22(b), the positive electrodes of the four sets of batteries located on the left are connected to the positive terminal 107a, and the positive terminal 107a outputs a voltage of 1"V1". The positive electrodes of the two sets of batteries located on the right side of the figure are connected to the positive terminal 107b, and the positive terminal 107b outputs a voltage of 2"V2". However, in the embodiment of Figure 22(b), since the number of battery stages is the same at 2 stages, there is no difference between voltages V1 and V2. To make voltages V1 and V2 different, the number of stages of battery B must be different.

[0142] Furthermore, if negative terminal 104a is designated as "GND1" and negative terminal 104b is designated as "GND2", it goes without saying that voltages "V1" and "V2" can be made to have different potentials. Figure 23 is a block diagram and explanatory diagram relating to the circuit or control of the electric bicycle and electric assist bicycle of the present invention.

[0143] In Figure 23, battery unit 307 is a battery unit consisting of the zinc (secondary) battery 500 of the present invention. Battery unit 308 is a battery unit consisting of a lithium-ion secondary battery. In addition, a large-capacity capacitor 507 is included to handle steep current output.

[0144] Electric bicycles and electric assist bicycles are equipped with motor 501. Motor 501 is a three-phase brushless motor and is located on the front wheel. However, motor 501 is not limited to a three-phase brushless motor. A two-pole DC motor 501 or the like may also be used. The electric vehicle and electric assist bicycle of the present invention are equipped with a regenerative charging function that charges the battery unit 307 with electricity generated from the motor 501 during braking.

[0145] For example, when a rider is operating an electric bicycle, if they apply the brakes, the regenerative braking charging function is activated, and the electricity generated from the motor 501 charges the battery unit 307.

[0146] The drive control circuit 506 is fitted with or positioned a position detection sensor 502 for the motor 501 (which performs functions such as detecting the rotation state and measuring the rotation speed). The output of the position detection sensor 502 is input to a vehicle speed input circuit (not shown).

[0147] The inverter circuit 504 includes an H-side FET (Ssu) and an L-side FET (Smu) for switching the U-phase of the motor 501, an H-side FET (Ssv) and an L-side FET (Smv) for switching the V-phase of the motor 501, and an H-side FET (Ssw) and an L-side FET (Smw) for switching the W-phase of the motor 501.

[0148] The H side is sometimes called the upper side, and the L side is sometimes called the lower side. The inverter circuit 504 is equipped with a temperature sensor 503a, and the motor 501 is equipped with a temperature sensor 503b.

[0149] The inverter circuit 504 is connected to one end of the capacitor 507, and the other end of the capacitor 507 is grounded. The capacitance of the capacitor 507 is relatively large.

[0150] The switch circuit 505 is located between the inverter circuit 504 and the battery unit, and operates to isolate the battery unit from the inverter circuit 504 in response to instructions from the drive control circuit 506. It also electrically connects the battery unit and the inverter circuit 504.

[0151] By controlling the on-time of the transistor in the inverter circuit 504, the power applied to the motor 501 can be adjusted. Furthermore, the voltage (power) generated by the motor 501 can be adjusted.

[0152] The switch circuit 505 is connected to the inverter circuit 504. A current sensor 508 is placed in the power path to the inverter circuit 504, allowing for the measurement of the input current and output current to the inverter circuit 504. The operation (open / closed) of switches SWa and SWb in the switch circuit 505 is varied or set based on the current value measured by the current sensor 508.

[0153] Lithium-ion batteries are susceptible to overcharging and over-discharging. Furthermore, because the electrolyte liquid is flammable, high temperatures can cause violent chemical reactions inside, leading to ignition. At sub-zero temperatures, not only does the discharge capacity decrease, but the electrolyte liquid can freeze, damaging the internal components and potentially leading to fire.

[0154] Zinc-ion batteries use an aqueous electrolyte, making them highly safe. Furthermore, zinc-ion batteries are highly recyclable and have an energy density approximately twice that of lead-acid batteries. However, repeated charging and discharging can cause zinc to precipitate from the negative electrode, potentially leading to a short circuit with the positive electrode.

[0155] The battery housing 509 of the present invention has a battery unit 307 made of a zinc secondary battery and a battery unit 308 made of a lithium-ion battery. A temperature sensor 503c is located in the battery housing 509. The temperature sensor 503c measures the temperature of the battery housing 509.

[0156] If the temperature is within a predetermined range, the switch SWa of the switch circuit 505 is turned on, and power from the battery unit 308, which consists of a lithium-ion battery, is used. Also, if there is a large change in the output current, power from the battery unit 308 is used.

[0157] If the temperature is above or below a predetermined value, switch SWb of the switch circuit 505 is turned on, and power from the battery unit 307, which consists of a zinc secondary battery, is used. Also, if the output current is stable and large, power from the battery unit 307 is used. If a large output current is required, both switches SWa and SWb of the switch circuit 505 are turned on. [Industrial applicability]

[0158] The zinc secondary battery of this invention enables faster charging and discharging compared to lithium-ion batteries and the like. It also exhibits excellent high-power characteristics. It is expected to have applications in various fields, such as energy storage for new energy sources.

[0159] Furthermore, because the solvent is water, it is highly safe, non-volatile, easy to manage moisture content, and low-cost. It also does not experience short-circuit failures, has a long lifespan, and is expected to be used in a variety of fields. [Explanation of Symbols]

[0160] 101 Battery container 102 Negative electrode 103 Negative electrode material 104 negative terminal 105 Positive electrode 106 Cathode material 107 Positive terminal 108 Electrolyte 109 Separator 110 Conductive layer 111 Conductive terminals 112 (Variable) Voltage (Current) Source 114 Switch Circuit 115 Insulating layer 116 Resistance meter 117 Pulse Generator 201 Negative Electrode Case 202 Positive Electrode Case 203 Gasket 204 Insulating film 205 Dendrites 206 Small hole 207 Elastic body 208 Pressure Cap 209 Pressing part 301 Battery Box 302 Spring fittings 303 Connecting fittings 304 Rotating body 305 Convex part 306 Connection Wiring 307 Battery Unit 308 Battery Unit 500 batteries 501 Motor 502 Position detection sensor 503 Temperature Sensor 504 Inverter Circuit 505 Switch Circuit 506 Drive Control Circuit 507 Capacitor 508 Current Sensor 509 cabinets

Claims

[Claim 1] Positive electrode material, A negative electrode material containing zinc, A separator having a conductive layer, An electrolyte solution for permeating the positive electrode material and the negative electrode material, The system includes a power supply device that applies current or voltage between the negative terminal and the conductive terminal, The positive terminal is connected to the positive electrode material. The negative terminal is connected to the negative electrode material. A zinc secondary battery characterized in that conductive terminals are connected to the conductive layer.

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