A hydrogen ion battery based on titanium negative electrode and preparation method thereof

Abstract

The present invention relates to a hydrogen ion battery based on a titanium negative electrode and a method for preparing the same. The battery comprises a negative electrode, a positive electrode, an electrolyte, and a separator disposed between the positive and negative electrodes. The active material of the negative electrode contains one or more of titanium elements Ti(IV) / Ti(III) oxides, complex salts, and hydrates thereof, oxyhydroxides, complex salts, and hydrates thereof, and hydroxides, complex salts, and hydrates thereof. The active material of the battery's positive electrode contains one or more of manganese or nickel oxides, complex salts, and hydrates thereof, oxyhydroxides, complex salts, and hydrates thereof, and hydroxides, complex salts, and hydrates thereof. The separator is a corrosion-resistant porous material. An alkaline aqueous solution with a pH of 7 to 13 is used as the battery electrolyte. Compared with the prior art, the battery of the present invention has a simple structure, low material, manufacturing, and operating costs, high energy efficiency and cycle life, and good safety, making it suitable for large-scale power storage.

Claims

1. A hydrogen ion battery based on a titanium negative electrode, comprising a negative electrode, a positive electrode, an electrolyte, and a separator disposed between the positive and negative electrodes; characterized in that: The active material of the negative electrode contains one or more of titanium element Ti(IV) / Ti(III) oxides and their double salts and hydrates, oxyhydroxides and their double salts and hydrates, hydroxides and their double salts and hydrates; Among them, the oxides and their double salts and hydrates, oxyhydroxides and their double salts and hydrates, and hydroxides and their double salts and hydrates containing titanium element Ti(IV) include the following chemical formulas: Uncle p (OH) q THE a · G, Oxides and double salts and hydrates thereof, oxyhydroxides and double salts and hydrates thereof, hydroxides and double salts and hydrates thereof containing titanium element Ti(III) include the following chemical formulas: Uncle p-1 (OH) q+1 THE a · G, Among them: 1≤p≤2, 0≤q≤2, a=4-2p-q≥0, A = HCO3 - 、(CO3 2- ) 1 / 2 、NO3 - 、(SO4 2- ) 1 / 2 、ClO4 - 、C6H5SO3 - Any one or a mixture of any several of the anions, the molar ratio of the mixture is 0~1:0~1:0~1:0~1:0~1:0~1, and not all of them are 0; G = M m E n O x (OH) y A z ·t(H2O), where 0 ≤ m, n, x, z, t ≤ 5 and m and n are not both 0, 0 < y ≤ 10, M is any one or any mixture of Mg, Ca, Fe(II), and the molar ratio of the mixture of Mg, Ca, Fe(II) is 0~1:0~1:0~1:0~1, E is any one or any mixture of Al, Fe(III), and the molar ratio of the mixture of Al, Fe(III) is 0~1:0~1 and they are not both 0; The active substance in the positive electrode material includes manganese or nickel.

2. The hydrogen ion battery based on titanium negative electrode according to claim 1, characterized in that The electrolyte is an aqueous solution with a pH of 7 to 13, and the anions in the electrolyte are: OH - 、HCO3 - 、CO3 2- 、NO3 - 、SO4 2- 、ClO4 - 、C6H5SO3 - Any one or more of the following, the anion concentration is 0~5mol / L, and not 0 at the same time; the corresponding cation is: H + 、Na + Mg 2+ , K + , Ca 2 + Any one or a mixture of several thereof, the molar ratio of the mixture is 0~1:0~1:0~1:0~1:0~1, and cannot be 0 at the same time.

3. The hydrogen ion battery based on titanium negative electrode according to claim 1 or 2, characterized in that The TiO p (OH) q A a G is prepared by co-precipitation or ball milling: Co-precipitation method: According to TiO p (OH) q A a A titanium (IV) precursor and a precursor containing element M or element E are weighed and mixed, and a soluble base is added. The resulting precipitate is filtered and washed to obtain titanium (IV) oxides, double salts and hydrates thereof, oxyhydroxides, double salts and hydrates thereof, and hydroxides, double salts and hydrates thereof; Ball milling method: According to TiO p (OH) q A a · G, weighing a titanium element Ti(IV) precursor, adding a soluble base, filtering and washing the resulting precipitate to obtain TiO2·wH2O, wherein 0≤w<3; mixing the obtained TiO2·wH2O or commercially available TiO2 with Mg(OH)2, a magnesium salt and H2O in a molar ratio of 1:0.1~5:0.01~1:0.01~10, and ball milling for 1 minute to 100 hours; filtering and washing the resulting product to obtain the oxide and its complex salt and hydrate, oxyhydroxide and its complex salt and hydrate, and hydroxide and its complex salt and hydrate containing the titanium element Ti(IV); The TiO p-1 (OH) q+1 A a G is prepared by co-precipitation method: adding iron powder, zinc powder or a mixture of the two to a titanium (IV) precursor, wherein the sum of the amount of Fe and Zn is equal to the amount of Ti 4+ or TiO 2+ The molar ratio is 1:0.5~2; after being fully stirred for 1min~50h, the Ti 4+ or TiO 2+ Reduction to Ti 3+ After filtering out the remaining iron powder or zinc powder, a precursor containing the M element or a precursor containing the E element is added under the protection of a non-oxidizing gas; under the protection of a non-oxidizing gas, a soluble base is added with sufficient stirring; the resulting precipitate is filtered and washed to obtain the oxide and its complex salt and hydrate, oxyhydroxide and its complex salt and hydrate, hydroxide and its complex salt and hydrate containing the titanium element Ti(III).

4. The hydrogen ion battery based on titanium negative electrode according to claim 1, characterized in that: The negative electrode is prepared by wetting the negative electrode material with electrolyte and then applying the electrolyte to the surface of a graphite carbon electrode, a stainless steel electrode or a titanium electrode.

5. The hydrogen ion battery based on titanium negative electrode according to claim 3, characterized in that: The negative electrode material also includes graphitized particles or fiber materials.

6. The hydrogen ion battery based on titanium negative electrode according to claim 1, characterized in that: The positive electrode of the battery is prepared by wetting the positive electrode material with electrolyte and then applying it to the surface of graphite carbon electrode, stainless steel electrode or titanium electrode. The active material in the positive electrode material includes one or more of manganese element Mn(IV) / Mn(III) / Mn(II) oxides and their double salts and hydrates, hydroxy oxides and their double salts and hydrates, hydroxides and their double salts and hydrates, or a mixture thereof with graphitized particles or fiber materials.

7. The hydrogen ion battery based on titanium negative electrode according to claim 1, characterized in that: The positive electrode of the battery is prepared by wetting the positive electrode material with electrolyte and then applying it to the surface of graphite carbon electrode, stainless steel electrode or titanium electrode. The active material in the positive electrode material includes one or more of nickel element Ni(IV) / Ni(III) / Ni(II) oxides and their double salts and hydrates, oxyhydroxides and their double salts and hydrates, hydroxides and their double salts and hydrates; or a mixture thereof with graphitized particles or fiber materials.

8. The hydrogen ion battery based on titanium negative electrode according to claim 1, characterized in that: The diaphragm is a corrosion-resistant porous material, including one or a composite of porous polymer film, non-woven fabric, filter paper.

9. A method for preparing a hydrogen ion battery based on a titanium negative electrode according to claim 1 or 2, characterized in that: The positive and negative active materials are placed inward and sandwiched on both sides of the separator to form a single cell; multiple single cells are stacked and assembled in parallel or rolled into a column to form a battery core pack, which is then encapsulated in a corrosion-resistant battery shell to produce a hydrogen ion battery pack.

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