WO2011079482A1 - Battery - Google Patents

Abstract

The present invention belongs to the field of electrochemical energy storage and discloses a battery. Said battery includes positive electrode, negative electrode and electrolyte. The active material of positive electrode uses a kind of material capable of reversible intercalation and deintercalation. The negative electrode uses metal. The electrolyte uses the solution comprising the ion capable of intercalation and deintercalation in the positive electrode and the ion of negative electrode metal. The reversibility of the positive electrode of the battery is dependent on the ion intercalation or deintercalation in the positive active material. The reversibility of the negative electrode is dependent on the electro-deposition and dissolution of the metal ion in the surface of negative electrode. The battery of the present invention is more environmentally friendly than lead acid battery. Said battery is cheaper and has higher energy density than the battery using nickel as positive electrode. Said battery does not have the problem of self-discharge which exists in zinc- bromine cell and is more inexpensive than Li-ion battery. Said battery is convenient for fabrication and maintenance and can be expected to replace the lead acid battery in a short time and to be applied to electric-vehicles and large-scale energy storage projects.

Description

 Battery technology field

 The invention belongs to the field of electrochemical energy storage, and particularly relates to a battery. Background technique

 Today, chemical energy is becoming scarcer, and the development of electric vehicles and wind energy is imminent. Although the fields of motors, propellers and the like are very mature, there has been no breakthrough in the field of energy storage, which limits the wide range of applications such as electric vehicles and wind energy.

 Rechargeable batteries that have been commercially used in history include lead-acid batteries, nickel-cadmium batteries, nickel-hydrogen batteries, lithium-ion batteries, etc., as well as nickel-zinc batteries, zinc-bromine batteries, etc., which are not fully mature. At present, lead-acid batteries and nickel-cadmium batteries are not accepted because of serious pollution and toxic. Nickel-hydrogen batteries are still too expensive, and nickel resources are not rich, which limits their development. Nickel-zinc batteries have been extensively studied in the 1960s and 1970s, but in alkaline environments, the dissolution of zinc anodes and the growth of dendrites are not effectively controlled, so it has been difficult to mature. The problems encountered by zinc-bromine batteries are the diffusion of bromine, self-discharge and other factors. At present, zinc-bromine batteries have already had a certain scale of demonstration operation in developed countries, but there is still a long way to go before practical applications. At the same time, the energy density of batteries designed for large-scale energy storage projects is too low, and it is not suitable for mobile power sources like electric vehicles.

 At present, batteries for electric vehicles are also fuel cells and metal air batteries. Among them, fuel cells have powerful power and energy density close to that of internal combustion engine systems. However, after nearly 20 years of research on fuel cells, they have not made breakthroughs in key technologies, and still need to use precious metal catalysts such as platinum. Before the breakthrough of key technologies, its expensive price and scarcity of platinum resources made it destined to be unusable for a short time. It can be said that the fuel economy has stalled, leading to the collapse of the US hydrogen economy. Other types of batteries, such as zinc-air batteries, are primary batteries that are difficult to use widely.

Lithium-ion batteries have been widely used since they were commercialized in the early 1990s. The principle of such a battery is to obtain a potential difference by different deintercalation-insertion reaction potentials of lithium ions in the positive and negative active materials, and lithium ions flow between the positive and negative electrodes during charging and discharging, which is called a rocking chair battery. Since the charging voltage is high, the electrolyte can only use an organic solution which is stable over a wide voltage range as an electrolyte, and accordingly a suitable electrolyte is also very limited. With the increase of energy density, the improvement of rate discharge performance and the improvement of safety performance brought by new cathode materials, lithium-ion batteries have gradually become more and more applicable in power tools, electric vehicles, and large-scale energy storage batteries. Current most It is possible to use lithium-ion batteries with lithium iron phosphate or lithium manganate as cathode materials for applications in electric vehicles and energy storage projects. However, such batteries are still not fully mature, mainly because they are expensive, and the control of moisture during the manufacturing process also leads to additional cost and instability of product consistency. These two factors have greatly hindered the large-scale application of lithium-ion batteries. In order to improve the safety of lithium ion secondary batteries and reduce the cost of batteries, many researchers are currently working on the research of water-based lithium-ion batteries, such as LiMn ₂ O ₄ as the positive electrode and vanadium oxide such as LiV ₃ O ₈ as the negative electrode. The principle of the rocking chair battery appears, but the development of such batteries is limited by the poor cycle performance of the negative electrode and the toxicity of vanadium. Up to now, the structure of the water-based lithium ion secondary battery that has been proposed has not been shaken off from the rocker-type structure based on the principle of lithium ion deintercalation, such as VO ₂ / LiMn ₂ O ₄ , LiV ₃ O ₈ / LiNi ₈₁ Co which have been reported. ₁₉ O ₂ , TiP ₂ O ₇ /LiMn ₂ O ₄ , LiTi ₂ (PO ₄ ) ₃ /LiMn ₂ O ₄ , LiV ₃ O ₈ /LiCoO ₂ and the like. Summary of the invention

 In view of the shortcomings and deficiencies of batteries that have historically appeared, the inventors aimed to develop a new battery, a new secondary battery. The battery has high energy density (up to 60%-80% of lithium ion battery), high power density (expected to reach 200% of lithium ion battery, or even higher), easy to manufacture (no water is needed in the manufacturing process) Control), completely non-toxic, environmentally friendly, easy to recycle and low cost (the same capacity of the battery, is expected to reach 60% of lead-acid batteries, 20% of lithium-ion batteries, or even lower).

 In order to achieve the object of the present invention, the inventors provide the following technical solutions:

 A battery comprising a positive electrode, a negative electrode and an electrolysis, wherein the active material of the positive electrode is one of a material capable of reversibly extracting-embeding ions or functional groups, and at least one of the metal elements is negatively used, and the electrolyte is capable of dissolving the electrolyte. At least one of a solvent which is ionized, wherein the electrolyte contains a metal ion of a positive electrode which can be eluted-embedded ions and a negative electrode active material. In the battery of the present invention, the reversibility of the positive electrode is achieved by the extraction or embedding of the detachable-embedded ions on the positive active material, and the reversibility of the negative electrode is achieved by electrochemical oxidation and reduction of the metal ion on the surface of the negative electrode. .

 The battery of the present invention includes a positive electrode, a negative electrode and an electrolyte in its core structure. The active material of the positive electrode is a compound capable of eluting-intercalating lithium ions or sodium ions; the negative electrode is a pure metal plate/foil, or a formed metal powder, and the metal is an active material of a negative electrode and can also serve as a negative electrode The fluid is a solvent capable of dissolving the electrolyte and ionizing the electrolyte, such as water, an alcohol (such as methanol, ethanol), or the like, or another organic solvent capable of dissolving the electrolyte and ionizing the electrolyte, wherein the electrolyte A metal ion containing an ion-decomposing ion and a negative electrode active material which can be extracted in the positive electrode material.

The positive electrode active material of the battery of the present invention is a compound capable of eluting-embedding ions, and the negative electrode active material is a metal having a different oxidation-reduction potential from the positive electrode active material deintercalation potential. During discharge, the positive electrode acquires electrons and intercalates ions; the negative active material metal loses electrons and dissolves in the electrolyte. The electrolyte is a solution of multiple ions, Includes ions that can be deintercalated from the cathode material, to! a salt, a hydroxide, or other soluble corresponding metal compound of a metal contained in the negative electrode active material. '

负极反应为 M^x++xe'→M， LiAaB_PC ¾— 种离子嵌入化合物的通式， M为一种金 ， 是一种或几种金属的离子形态。 ）， 正 极的锂离子或者其他可脱出-嵌入离子从正极活性物质中脱出，正极活性物质中的变价 离子被氧化并失去电子， 电子从正极经由外电路到达负极。 电解液中所包含的一种金 属离子在负极表面获得电子， 并以金属形态电沉积在负极表面， 从而实现充电。 放电 过程与充电过程相反。 The charging and discharging working principle of the battery of the invention is as follows: When charging (see Fig. 2A, in the figure, the positive electrode reaction is LiA _a B _e C — xe' - x

The negative electrode reaction is M ^x+ + xe' → M, LiAaB _P C 3⁄4 - the general formula of the ion intercalating compound, and M is a kind of gold, which is an ion form of one or several metals. Lithium ions or other detachable-embedded ions of the positive electrode are removed from the positive electrode active material, and the valence ions in the positive electrode active material are oxidized and lose electrons, and electrons pass from the positive electrode to the negative electrode via the external circuit. A metal ion contained in the electrolyte obtains electrons on the surface of the negative electrode and is electrodeposited on the surface of the negative electrode in a metal form to achieve charging. The discharge process is the opposite of the charging process.

负极反应为 Zn²⁺+xe'→ (x/2)Zn。 放电过程为充电过程的逆过程 即负极 0价锌的氧化并溶解， 正极获得了电 子并伴随锂离子插入 li^M^OA中， 放电时（如附图 2B-2所示）， 正极反应为 Taking LiMn ₂ O ₄ /Zn battery as an example (see Figures 2B-1 and 2B-2), the inventors further explain the working principle of the battery of the present invention: charging battery with LiMn ₂ O ₄ as positive electrode and zinc as negative electrode, charging When Li ⁺ ions in LiMn ₂ O ₄ are removed from the crystal lattice, one trivalent manganese loses an electron to be oxidized, LiMn ₂ O ₄ becomes a form of Li^Mi^O, and at the same time, zinc ions in the electrolyte get electrons. It is reduced and deposited on the surface of the metal zinc. When charging (as shown in Figure 2B-A), the positive reaction is

The negative electrode reaction is Zn ²⁺ + xe' → (x/2) Zn. The discharge process is the reverse process of the charging process, that is, the zero-valent zinc of the negative electrode is oxidized and dissolved, and the positive electrode obtains electrons and is inserted into the lithium-ion ICP, and when discharged (as shown in FIG. 2B-2), the positive electrode reaction is

Li!. _x Mn ₂ O4+ Li ⁺ +xe'—LiMn ₂ O ₄ , and the negative electrode reacts with Zn—xe_→(x/2)Zn ²⁺ .

Preferably, according to the invention, the reversible de-intercalation-intercalating material comprises a compound capable of deintercalating-embedded lithium, sodium plasma. The inventors have found that when the positive electrode active material of the present invention is a compound capable of eluting-intercalating lithium ions, such as LiMn ₂ O ₄ , LiFePO ₄ , LiCoO ₂ Li xPO ₄ , LiM _x SiO _y (wherein M is a variable metal) ) Binary materials or ternary material compounds. In addition, the inventors have also found that other kinds of lithium ions can be extracted-incorporated into compounds such as LiV ₃ 0 _{8 ,} etc., sodium ion-extractable-embedded compounds such as NaVPO ₄ F, and the like, and can be ejected-embedded. The ionic, functional group compounds all have similar functions and are also suitable for the positive electrode structure of the battery of the present invention.

 Preferably, the battery according to the present invention, wherein the extractable-intercalating lithium ion-containing compound is selected from the group consisting of a layered structural compound, a spinel structure compound or an olivine structure compound, and other lithium and sodium ions are detachable. At least one of the embedded compounds.

其中， 0<x≤2， 0<y<0.5, M选自 Co、 Ni、 Mn中至少一种， M' 选自 Mg、 Ti、 Cr、 V、 Zn、 Zr、 Si或 Ai中至少一种， 例如 LiFeSiO₄等。 A battery according to the present invention, wherein the layered structural compound has a general formula of

Wherein, 0<x≤2, 0<y<0.5, M is at least one selected from the group consisting of Co, Ni, and Mn, and M' is at least one selected from the group consisting of Mg, Ti, Cr, V, Zn, Zr, Si, or Ai. For example, LiFeSiO ₄ or the like.

More preferably, the battery according to the present invention, wherein the spinel structure compound has a general formula of Li _x Mn _y M _z O _k , wherein 0.5<x≤3, 0<y<3 0 ≤ z ≤ 3, 0 ≤ k ≤ 8, M is at least one selected from the group consisting of Mg, Ti, Cr, V, Zn, Zr, Si or Al. For example, LiV ₃ O ₈ , LiMnSiO ₄ and the like. As a more preferred embodiment, according to the invention, the battery of the olivine structure has a general formula of Li _x M ₂ _ _y M' _y (XO ₄ ) _n . Wherein, 0<x≤3 ^; , 0≤y≤2, l≤n≤3, M is a transition metal element, and M' is at least one selected from the group consisting of Mg, Ti, Cr, V or A1, and X is selected from S, P or Si. For example, Li ₃ V ₂ (PO ₄ ) ₃ .

 Preferably, the battery according to the present invention, wherein the negative electrode is made of a metal element selected from the group consisting of

Cu, Ag, Fe, Zn, Sn, Al or Ni may be specifically used as a negative electrode of a metal elementary plate, a foamed metal, or a shaped metal powder.

 Preferably, the battery according to the present invention, wherein the positive electrode of the battery comprises a current collector, which uses at least one of stainless steel, carbon fiber, graphite and other electrochemically stable electron good conductors. In addition, the inventors have also found that with a completely chemically inert carbon-based material as the positive current collector, the cycle performance of the battery is much better than that of stainless steel as the positive current collector.

 As a more preferable embodiment, the electrolyte is a chloride of lithium and a chloride of an anode active material.

 As a more preferable embodiment, the electrolyte is a sulfate of lithium and a sulfate of a negative electrode active material.

 More preferably, the electrolyte is water, and 1 M lithium ion and 5 M negative electrode active material ions are dissolved. As a more preferable embodiment, the electrolytic solution is methanol, and 1 M lithium ion and 5 M negative electrode active material ion are dissolved.

 As a more preferable embodiment, the electrolytic solution is ethanol, and 1 M lithium ion and 5 M negative electrode active material ion are dissolved.

As a preferred embodiment, the battery of the present invention is made of inexpensive LiMn ₂ O ₄ , a conductive agent, and a binder, and is bonded to a graphite current collector, conductive carbon paper, or the like as a positive electrode; and the metal zinc or zinc powder is a negative electrode. The electrolyte includes lM Li ⁺ ions and 5M Zn ²⁺ ions. The conductive agent is graphite and the binder is a PTFE emulsion.

 Preferably, in the battery of the present invention, when the interval between the positive electrode and the negative electrode is 2 to 10 mm, the separator may not be used.

 Preferably, when the battery of the present invention further comprises a separator, the separator is an organic or inorganic porous material, and the separator has a pore diameter of 0.001-1 μm.

 Compared with the prior art, the present invention has the following advantages:

Cycle life unit energy energy density resource rich environment friendly (time) cost* *=:* sex as a power battery lead-acid battery 300 30% 30% rich, lead toxic for the previous generation mass production battery NiMH battery 1000 80% 60% Nickel resources are not nickel for toxic and bare nickel-cadmium batteries 1000 50% 40% Nickel resources are not impossible Nickel-zinc battery 300 30% 50% Nickel resources are not temporarily unavailable Zinc-bromine battery 2000 30% 40% Rich, bromine corrosive can not be mass produced temporarily

 Lithium-ion battery 2000 100% 100% rich, relatively friendly

 Mass production

 The battery of the invention 1000 or more 20% 60%-70% rich, can be very friendly

 Mass production

 *Remarks: The unit energy cost is calculated based on the current lithium battery.

 **Remarks: The energy density is calculated as 100% of the current lithium battery.

 In addition, the battery of the present invention is easy to manufacture, requires no moisture control during the manufacturing process, is easy to recycle, and is inexpensive.

(The same capacity battery is expected to reach 60% of lead-acid batteries, 20% of lithium-ion batteries, or even lower)

 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the structure of a battery of the present invention, wherein 1 is a positive electrode current collector, 2 is a positive electrode active material, 3 is a negative electrode active material as a current collector, and 4 is an electrolyte solution.

2A is _a schematic view showing the charging operation principle of the battery of the present invention in which the positive electrode material is LiA _a B _e C _A .

2B-1 and 2B-2 are schematic diagrams showing the working principle of the LiMn ₂ O ₄ /Zn battery of the present invention, wherein FIG. 2B-1 is a schematic diagram of a battery charging process; and FIG. 2B-2 is a schematic diagram of a battery discharging process.

3 is a graph showing the first charge and discharge of a LiMn ₂ O ₄ /Zn battery according to Embodiment 1 of the present invention, wherein 1 is a charge profile and 2 is a discharge curve. "

Figure 4 is a graph showing the cycle performance of a LiMn ₂ 04/i3⁄4 battery of Example 1 of the present invention.

Figure 5 is a graph showing the cycle performance of a LiFePO ₄ /Zn battery according to Example 3 of the present invention.

 Fig. 6 is a graph showing the cycle performance of a NaVPO^/Zn battery of Example 4 of the present invention.

Figure 7 is a graph showing the cycle performance of a LiMn ₂ O ₄ /foam nickel battery of Example 7 of the present invention.

Figure 8 is a graph showing the cycle performance of a LiMn ₂ O ₄ /Zn battery according to Example 14 of the present invention.

Figure 9 is a graph showing the relationship between charge and discharge efficiency and charge current multiplication of LiMn ₂ O ₄ /Zn battery in Example 20 of the present invention.

detailed description

 The contents of the present invention will be more specifically described below with reference to the embodiments. It is to be understood that the invention is not limited to the embodiments described below, and any form of modifications and/or changes made to the invention are intended to fall within the scope of the invention.

In the present invention, unless otherwise specified, all parts and percentages are by weight, all equipment and raw materials, etc. Can be purchased from the market or commonly used in the industry example 1

LiMn ₂ 0 ₄ is used as the positive electrode active material, and is uniformly mixed according to the positive electrode active material 88 wt%: conductive carbon black 8 wt%: adhesive PTFE (polytetrafluoroethylene) 4 wt%, and cut into a diameter of 12 mm and a thickness of 0.1-0.2 mm. The wafer is pressed onto a graphite current collector to form a positive electrode. The negative electrode active material was metal zinc having a width of 15 mm and a thickness of 1 mm, and also served as a current collector. The positive and negative electrodes are separated by 5 mm and have no diaphragm. The electrolytic solution was a mixed aqueous solution of lithium chloride and zinc chloride containing 1 mol/L of lithium ion and 5 mol/L of zinc ion. The cycle test was carried out under a voltage range of U-2.05 V and a charge-discharge current of 0.5 C. Figure 1 shows the basic structure of a battery. The first charge and discharge curve is shown in Figure 3, and the battery cycle performance is shown in Figure 4. It can be seen that the charge and discharge curve of the battery is very similar to that of the lithium ion battery of the organic electrolyte system, except that the platform is lower. From the perspective of the test battery, the cycle performance is also excellent.

 Example 2

A battery was fabricated in the same manner as in Example 1, except that LiCoO _{2 was} used as the positive electrode active material, and the cycle operating voltage ranged from 1.3-1.95 V. The battery cycle performance test results are shown in Table 1.

 Example 3

A battery was fabricated in the same manner as in Example 1, except that LiFePO _{4 was} used as the positive electrode active material, and the cycle operating voltage ranged from 0.8 to 1.6 V. The battery cycle performance test results are shown in Table 1 and Figure 5.

 Example 4

A battery was fabricated in the same manner as in Example 1, except that NaVPO ₄ F was used as a positive electrode active material, and the cycle operating voltage ranged from 1.3 to 2.0 V. The battery cycle performance test results are shown in Table 1 and Figure 6.

 Example 5

A battery was fabricated in the same manner as in Example 1, except that LiMn ₂ 0 ₄ and LiCo0 ₂ were mixed at a mass ratio of 1:1 as a positive electrode active material, and the cycle operating voltage ranged from 1.3 to 2.05 V. The test results of charge and discharge and battery cycle performance are shown in Table 1. Capacity retention test

 The batteries of the above Examples 1-5 were subjected to a cyclic charge discharge operation to detect the battery capacity retention rate after 30 cycles. First, the battery is charged at a fixed current of 0.5 C rate until the voltage reaches the upper limit, and then the battery is discharged at a fixed current of 0.5 C rate until the voltage reaches the lower limit. So repeating this week.

 Table 1 below shows the battery performance exhibited by several different positive electrode materials and metallic zinc as counter electrodes.

Table 1 Positive active negative electrode active as voltage open circuit voltage for the first time average 30 weeks of material retention 3⁄4 surrounding discharge voltage holding rate Example 1 LiMn ₂ 0 ₄ 1.3-2.05V 2.0 1.8 92% Example 2 LiCo0 ₂ 1,3-1.95V 1.9 1.7 94 % Example 3 LiFeP0 ₄ metal zinc plate 0: 8-1.6 V 1.5 1.2 82% Example 4 NaVP0 ₄ F 1.3-2.0 V 1.8 1.4 44% Example 5 LiMn ₂ 0 ₄ and 1.3-2.05 V 2.0 1.7 91%

LiCo0 ₂

Among them, LiMn ₂ O _{4 is} used as the positive electrode active material, and the first charge and discharge curve of the metal zinc as the counter electrode is shown in FIG. 3 , and the cycle performance of the battery is shown in FIG. 4 . According to the results shown in Table 1, it can be seen that for the more mature cathode materials (LiMn ₂ 0 ₄ , LiCo0 ₂ and LiMn ₂ 0 ₄ /LiCo0 ₂ ), the electrochemical performance is better than that of other materials (LiFeP0 ₄ , NaVP0 _{4 ).} F) It is much better.

 Example 6

LiMn ₂ 0 ₄ is used as the positive electrode active material, and is uniformly mixed according to the positive electrode active material 88 wt %: conductive carbon black 8 wt %: adhesive PTFE 4 wt%, and cut into discs having a diameter of 12 mm and a thickness of 0.1-0.2 mm, and pressed at On the graphite current collector, the positive electrode is formed; the negative electrode active material is a manganese-coated zinc plate having a width of 15 mm and a thickness of 0.5-lmm (wherein the reduction property of zinc is not as strong as that of manganese, and does not participate in the reaction during charge and discharge, but acts as a current collector). The positive and negative electrodes are separated by 5 mm and have no diaphragm. The electrolytic solution was a mixed aqueous solution of lithium chloride and manganese chloride containing 1 md/L of lithium ion and 5 mol/L of manganese ion. The cycle test was performed with a voltage range of 1.3-2.2 V and a charge-discharge current of 0.5 C.

 Example 7

 A battery was fabricated in the same manner as in Example 6, except that instead of a manganese-coated zinc plate as a negative electrode, a nickel chloride containing 5 mol/L of nickel ions was replaced by nickel chloride containing 5 mol/L of nickel ions. The aqueous solution was used as an electrolyte for a cycle test between a voltage range of 0.8-L5V and a charge-discharge current of 0.5C. The results of the battery cycle performance test are shown in Table 2 and Figure 7.

 Example 8

 A battery was fabricated in the same manner as in Example 6, except that an iron sheet was used instead of the manganese-coated zinc plate as the negative electrode, and accordingly, an aqueous solution of manganese chloride containing 5 mol of L manganese ions was replaced by ferric chloride containing 5 mol of iron ions. The liquid is subjected to a cycle test in a voltage range of 1.3 to 2.0 V and a charge and discharge current of 0.5 C.

 Example 9

A battery was fabricated in the same manner as in Example 6, except that a cadmium sheet was used instead of the manganese-coated zinc sheet as a negative electrode, and a calcium chloride solution containing 5 mol/L of manganese ions was replaced by cadmium chloride containing 5 mol/L of cadmium ions. As the electrolytic solution, a cycle test was performed with a voltage range of 1.3 to 2.0 V and a charge and discharge current of 0.5 C. A battery was fabricated in the same manner as in Example 6, except that the pressed zinc powder was used instead of the manganese-coated zinc sheet as the negative electrode, and the test method was the same as in Example 2.

 Example 11

 A battery was fabricated in the same manner as in Example 6, except that zinc oxide was used instead of the manganese-coated zinc sheet as the negative electrode, and the test method was the same as in Example 2.

 Capacity retention test

 The batteries in the above Examples 1 and 6-11 were subjected to a cyclic charge discharge operation to detect the capacity retention rate after 30 cycles. First, the battery is charged at a fixed current of 0.5 C rate until the voltage reaches the upper limit, and then the battery is discharged at a fixed current of 0.5 C rate until the voltage reaches the lower limit. So repeating this week.

Table 2 below shows the battery performance exhibited by the negative electrodes of several different metals and LiMn ₂ O ₄ as the positive electrode active material counter electrode.

 Table 2

 It can be seen that the cycle performance of the battery composed of metal zinc, zinc powder, zinc dioxide and nickel metal as the negative electrode is the best, but the voltage of the nickel negative electrode is low. For negative, its reversibility directly affects the cycle performance of the battery. As a mature, more studied anode, zinc has a significantly better cycle performance than several other materials.

 Example 12

 A battery was fabricated in the same manner as in Example 1, except that an aqueous solution of lithium acetate containing 1 mol of lithium ion and zinc acetate containing 3 mol/L of zinc ion was used as an electrolytic solution, and the cycle operating voltage range was 1.3-2.05V.

 Example 13

 A battery was fabricated in the same manner as in Example 1, except that lithium acetate containing 1 mol/L of lithium ion and methanol solution of zinc acetate containing 3 mol/L of zinc ion were used as the electrolyte, and the cycle operating voltage range was 1.3-2.05V. .

Example 14 A battery was fabricated in the same manner as in Example 1, except that lithium acetate containing 1 mol/L of lithium ion and ethanol solution of zinc acetate containing 3 mol/L of zinc ion were used as a solution, and the cycle operating voltage range was 1.3-2.05. V. The battery cycle performance test results are shown in Table 3 and Figure 8. ;

 Example 15

 A battery was fabricated in the same manner as in Example 1, except that an aqueous solution of lithium sulfate containing 1 mol/L of lithium ion and zinc sulfate containing 5 mol/L of zinc ion was used as an electrolytic solution, and the cycle operating voltage range was 1.3-2.05V.

 Capacity retention test

 The test was carried out in the same manner as in Example 1. The battery electrical properties are shown in Table 3.

 table 3

 It can be seen that the batteries in different electrolytes exhibit slightly different electrochemical properties. For the battery of the present invention, water, methanol or ethanol is suitable as the electrolyte. The cycle performance of Example 14 is shown in Figure 8.

 Example 16

 A battery was fabricated in the same manner as in Example 1, except that a 316L type stainless steel having a thickness of 1 mm was used instead of the graphite sheet as a positive electrode active material current collector.

 Example 17

 A battery was fabricated in the same manner as in Example 1, except that a 304 type stainless steel having a thickness of 1 mm was used instead of the graphite sheet as a positive electrode active material current collector. '

 Example 18

 A battery was fabricated in the same manner as in Example 1, except that a carbon fiber cloth (thickness of about 0.1 mm) was used instead of the graphite sheet as a positive electrode active material current collector.

 Capacity retention test

The test was carried out in the same manner as in Example 1. The battery electrical properties are shown in Table 4. Table 4

 From the results shown in Table 4, it can be seen that the cycle performance of a battery using a completely electrochemically inert carbon-based material as a current collector is much better than that of using a stainless steel as a current collector.

 Example 19

 The inventors have also examined the electrical properties of a variety of other lithium ion-embedded compounds and metals as counter electrodes. Although the cycle performance of these combinations is quite different, they all form batteries and the charge and discharge mechanisms are basically the same, which are in accordance with the principle of charge and discharge of the battery of the present invention. Table 5 shows the discharge open circuit voltages of the batteries composed of various electrode compositions.

 Table 5 shows the open circuit voltage of the battery with different positive and negative poles

 The positive and negative electrodes listed in Table 5 are only a small portion of the positive and negative electrodes that may be used in the battery of the present invention. Since there are many possible forms of such batteries in accordance with the principles of the present invention, particularly positive electrode materials, it may include sodium ion intercalation compounds which are not yet matured, as well as certain functional group deintercalation compounds and the like.

 Example 20

In an aqueous solution, the battery may be accompanied by a series of side reactions such as decomposition of water, etc., while charging the battery. A battery was fabricated in the same manner as in Example 1 to operate the battery at different charge and discharge current rates to obtain different charge and discharge current efficiencies. As a result, as shown in Fig. 9, a charge and discharge efficiency of 91% or more can be obtained at a suitable charge rate. Although the inventors have made a detailed description and enumeration of the technical solutions of the present invention, it should be understood that it is obvious to those skilled in the art that modifications and/or variations of the above-described embodiments or equivalent alternatives are apparent. The terminology used in the present invention is not to be construed as limiting the scope of the invention.

Claims

Claim A battery comprising a positive electrode, a negative electrode and an electrolyte, wherein the active material of the positive electrode is at least one of a material capable of reversibly eluting-embedding ions, and the negative electrode active material is at least one of metal simple substances. The electrolyte is at least one of a solvent capable of dissolving and ionizing the electrolyte, wherein the electrolyte contains a metal ion of the positive electrode extractable-embedded ion and the negative electrode active material.  2. A battery according to claim 1 wherein said reversibly detachable-embedded ion material comprises a compound which is capable of detaching - intercalating lithium ions or sodium ions. 3. The battery according to claim 2, wherein the extractable-intercalating lithium ion-containing compound is selected from the group consisting of a layered structural compound, a spinel structure compound, or an olivine structure compound; and a deionizable-embedded sodium ion The compounds include NaVPO ₄ F.  The battery according to claim 3, wherein the layered structural compound has a formula of LixMi.yM'yOz, wherein 0<x≤2, 0≤y≤l, M is selected from the group consisting of At least one of Co, Ni, and Μα, M' is at least one selected from the group consisting of Mg, Ti, Cr, V, Zn, Zr, Si, or Al. The battery according to claim 3, wherein the spinel structure compound has a general formula of Li _x Mn _y M _z O _k , wherein 0.5 < x ≤ 3, 0 < y < 3 0 < z < 3, 0 ≤ k ≤ 8, M is at least one selected from the group consisting of Mg, Ti, Cr, V, Zn, Zr, Si or Al. The battery according to claim 3, wherein the olivine structure compound has the formula Li _x M _1-y ' _y (XO ₄ ) _n , wherein 0 < x ≤ 3, 0 ≤ y ≤ 2, 1 < η < 3, M is a transition metal element, M' is at least one selected from the group consisting of Mg, Ti, Cr, V or Al, and X is selected from S, P or Si.  The battery according to claim 1, wherein the metal element is selected from the group consisting of Cu, Ag, Fe, Zn, Sn, Al or Ni.  8. A battery according to claim 1 wherein said electrolyte is a water or alcohol solution which dissolves and ionizes the electrolyte.  The battery according to claim 1, wherein the positive electrode of the battery comprises a current collector selected from at least one of stainless steel, carbon fiber, and graphite.  The battery according to claim 1, wherein the battery further comprises a separator which is an organic or inorganic porous material, and the separator has a pore diameter of 0.001-1 μm.