Titanic acid-sodium battery
By using sodium titanate as the positive electrode material, combined with graphite and polyaluminum trichloride electrolyte, the problem of low voltage in existing sodium titanate/sodium iron titanate batteries has been solved, realizing a sodium titanate battery with high energy density and good safety, lower cost and excellent performance.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-26
- Publication Date
- 2026-03-31
AI Technical Summary
Existing batteries using sodium titanate/sodium iron titanate as negative electrode materials have low voltage in "intercalation-deintercalation" batteries, resulting in extremely low energy density, which cannot meet high energy requirements.
Sodium titanate is used as the positive electrode material, combined with graphite as the negative electrode and polyaluminum trichloride as the electrolyte. The positive electrode material of sodium titanate battery is generated through specific temperature and reaction. Sodium hypochlorite and sodium chloride are used as synergists to increase the electrolyte concentration, forming a battery with lower cost and better safety performance.
It achieves a battery voltage of over 1V, with higher energy density and safety, lower cost, and is non-short-circuit, non-heating, non-combustible, and non-explosive.
Smart Images
Figure CN121769276A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of sodium titanate battery manufacturing technology, and in particular to a sodium titanate battery. Background Technology
[0002] In the current battery field, sodium titanate / sodium iron titanate is typically used as a negative electrode material and rarely as a positive electrode material. This is because in "intercalation-deintercalation" batteries, a suitable positive electrode material needs to have a high voltage to provide a sufficiently high operating voltage for the battery, thereby achieving high energy density.
[0003] When sodium titanate / sodium iron titanate is used as the positive electrode material in an intercalation-extraction battery, the assembled battery voltage is very low (a few tenths of a volt), which results in extremely low energy density.
[0004] To address this, the inventors developed a sodium titanate battery that uses sodium titanate / sodium iron titanate as the positive electrode material. The designed battery voltage can reach over 1V, providing a new approach to battery development. Summary of the Invention
[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide a sodium titanate battery that achieves a voltage of more than 1V when sodium titanate is used as the positive electrode material.
[0006] The objective of this invention is achieved through the following technical solution: a sodium titanate battery having a positive electrode, which is prepared from any of the following material combinations: The first type, by weight, includes 35.6 parts TiO2, 38.2 parts NaCl, and 26.2 parts ZnO; Alternatively, the second method, by weight, includes 25.6 parts TiO2, 38.2 parts NaCl, 10 parts Fe2O3, and 26.2 parts ZnO; Alternatively, the third type, by weight, includes 44.3 parts TiO2, 38.2 parts NaCl, and 17.5 parts Fe2O3; Alternatively, the fourth type, by weight, includes 34.3 parts TiO2, 38.2 parts NaCl, and 27.5 parts Fe2O3.
[0007] Furthermore, in the preparation of the positive electrode: if the first or second type is used as the positive electrode material, the powder of the corresponding material is mixed in a weight ratio and pressed into a block; then it is sent into the corresponding heating furnace and heated to 732°C and kept at a constant temperature for a period of time, then heated to 1100°C and kept at a constant temperature for a period of time; then the heating furnace is cooled to room temperature, and after the corresponding block is cooled down, it is taken out and soaked in clean water for a period of time to form the positive electrode.
[0008] Furthermore, in the preparation of the positive electrode: it is placed in a heating furnace and heated to 732°C, then heated to 1100°C and kept at a constant temperature for 1 hour; after the cooled block is taken out, it is soaked in clean water for 0.5 hours.
[0009] Furthermore, in the preparation of the positive electrode: if the third or fourth type is used as the positive electrode material, the powder of the corresponding material is mixed in a weight ratio and pressed into a block; then it is sent into the corresponding heating furnace and heated to 315°C and kept at a constant temperature for a period of time, then heated to 1100°C and kept at a constant temperature for a period of time; then the heating furnace is cooled to room temperature, and after the corresponding block is cooled down, it is taken out and soaked in clean water for a period of time to form the positive electrode.
[0010] Further, the material is heated in a furnace to 315°C, then heated to 1100°C and held at that temperature for 1 hour. After the cooled block is removed, it is soaked in clean water for 0.5 hours.
[0011] Furthermore, it also has an electrolyte, which is prepared from polyaluminum trichloride and water; wherein, polyaluminum trichloride accounts for 12%-15% of the total weight of the electrolyte.
[0012] Furthermore, when the electrolyte in the battery is insufficient, an enhancement solution is added after charging; the enhancement solution is prepared from sodium hypochlorite, sodium chloride, and water; wherein, sodium hypochlorite accounts for 15% of the total electrolyte weight and sodium chloride accounts for 7.5% of the total electrolyte weight.
[0013] Furthermore, the battery also has a negative electrode, which is a graphite tank containing electrolyte.
[0014] To facilitate understanding, the core working principle of this solution will be explained as follows: Sodium titanate was used as the positive electrode material, graphite was used as the negative electrode, and polyaluminum trichloride was used as the electrolyte. This method is more cost-effective. Specifically, when the first or second type is selected as the cathode material, during the sintering process in cathode preparation, when the temperature is raised to 732℃, the Na in NaCl... — Na is in a free state. — The material first reacts with ZnO to produce ZnCl and Na2O, and the boiling point of ZnCl is 732℃, so ZnCl is allowed to volatilize; then the temperature is raised to 1100℃, at which point Na2O reacts with the remaining substances to form the positive electrode; When the third or fourth type is selected as the cathode material, during the sintering process in cathode preparation, when the temperature is increased to 732℃, the Na in NaCl... — Na is in a free state. —The substance first reacts with Fe2O3 to produce Fe2Cl3 and Na2O, while FeCl3, with a boiling point of 315℃, is allowed to volatilize. Then, the temperature is raised to 1100℃, at which point Na2O reacts with the remaining substances to form the positive electrode.
[0015] The present invention has the following advantages: (1) Sodium titanate material was used as the positive electrode material of the battery; Specifically, this method can obtain sodium chloride from seawater or salt lake water (as a sodium source, the acquisition cost is low); then, using ZnO, ZnCl2 is obtained by reacting ZnO with sodium chloride. The chlorine element is removed by utilizing the characteristic of ZnCl2 evaporation at 732℃. Then, Na2O is reacted with the remaining substances to obtain the corresponding positive electrode material for sodium titanate batteries (or, using Fe2O3, FeCl3 is obtained by reacting Fe2O3 with sodium chloride. The chlorine element is removed by utilizing the characteristic of FeCl3 evaporation at 315℃. Then, Na2O is reacted with the remaining substances to obtain the corresponding positive electrode material for sodium titanate batteries). (2) This type of battery has a lower cost; Because it uses sodium titanate as the positive electrode, graphite as the negative electrode, and polyaluminum trioxide as the electrolyte, this battery has a lower cost. (3) The product does not short-circuit, does not heat up, does not burn, does not explode, and has excellent safety performance. Attached Figure Description
[0016] Figure 1 This is a voltage test diagram from Example 1; Figure 2 The current test diagram is shown in Example 1; Figure 3 This is a voltage test diagram from Example 2; Figure 4 The current test diagram is shown in Example 2; Figure 5 This is a voltage test diagram from Example 3; Figure 6 The current test diagram is shown in Example 3; Figure 7 This is a voltage test diagram from Example 4; Figure 8 This is the current test diagram for Example 4. Detailed Implementation
[0017] The present invention will be further described below, but the scope of protection of the present invention is not limited to the following description.
[0018] It should be noted that sodium titanate batteries, especially in sodium-ion battery systems, are receiving increasing attention due to their high safety, abundant raw materials, and low cost. The core of their preparation lies in the research and development and production of sodium titanate anode materials.
[0019] In sodium batteries, when sodium titanate is used as the negative electrode material, layered oxides (Na₂O₃) are typically employed. x TMO2 (TM is a transition element) or polyanionic compounds (Na) x M x (XO4) (where M is a transition metal and X is usually P, S, etc.) is used as the positive electrode. This type of battery is expensive.
[0020] This design uses sodium titanate as the positive electrode material, graphite as the negative electrode, and polyaluminum trichloride as the electrolyte. This type of battery has a lower cost.
[0021] (Example 1) This embodiment provides a sodium titanate battery, which has a positive electrode, a negative electrode, and an electrolyte.
[0022] The positive electrode, sodium titanate, is prepared using 35.6 parts TiO2, 38.2 parts NaCl, and 26.2 parts ZnO. The preparation process is as follows: ① First, the powders of each material are mixed according to the weight ratio and pressed into blocks; ② Then, the blocks are placed in a corresponding heating furnace and heated to 732℃ and held at that temperature for 1 hour, followed by heating to 1100℃ and holding at that temperature for another 1 hour, allowing the NaCl to react with the ZnO and the generated ZnCl to volatilize; ③ Then, the heating furnace is cooled to room temperature, and the blocks are removed and soaked in water for a period of time to form the positive electrode.
[0023] The obtained cathode material is .
[0024] The electrolyte is prepared using polyaluminum trichloride and water, with polyaluminum trichloride accounting for 12%-15% of the total electrolyte weight.
[0025] The negative electrode uses a graphite cell, which contains electrolyte.
[0026] It should be noted that when the electrolyte in this battery is insufficient, an enhancement solution should be added after charging. The enhancement solution is prepared from sodium hypochlorite, sodium chloride, and water; wherein, sodium hypochlorite accounts for 15% of the total electrolyte weight and sodium chloride accounts for 7.5% of the total electrolyte weight.
[0027] (Example 2) This embodiment provides a sodium titanate battery, which has a positive electrode, a negative electrode, and an electrolyte.
[0028] The positive electrode A1 is prepared using 25.6 parts TiO2, 38.2 parts NaCl, 10 parts Fe2O3, and 26.2 parts ZnO. The preparation process is as follows: ① First, the powders of each material are mixed according to the weight ratio and pressed into blocks; ② Then, the blocks are placed in a corresponding heating furnace and heated to 732℃ and held at that temperature for 1 hour, followed by heating to 1100℃ and holding at that temperature for another 1 hour, allowing NaCl to react with ZnO and the generated ZnCl to volatilize; ③ Then, the heating furnace is cooled to room temperature, and the blocks are removed and soaked in water for a period of time to form the positive electrode.
[0029] The obtained cathode material is Na5FeTi2O8.
[0030] The electrolyte is prepared using polyaluminum trichloride and water, with polyaluminum trichloride accounting for 12%-15% of the total electrolyte weight.
[0031] The negative electrode uses a graphite cell, which contains electrolyte.
[0032] It should be noted that when the electrolyte in this battery is insufficient, an enhancement solution should be added after charging. The enhancement solution is prepared from sodium hypochlorite, sodium chloride, and water; wherein, sodium hypochlorite accounts for 15% of the total electrolyte weight and sodium chloride accounts for 7.5% of the total electrolyte weight.
[0033] (Example 3) This embodiment provides a sodium titanate battery, which has a positive electrode, a negative electrode, and an electrolyte.
[0034] The positive electrode A2 is prepared using 44.3 parts TiO2, 38.2 parts NaCl, and 17.5 parts Fe2O3. The preparation process is as follows: ① First, the powders of each material are mixed according to the weight ratio and pressed into blocks; ② Then, the blocks are placed in a corresponding heating furnace and heated to 315℃, then further heated to 1100℃ and held at that temperature for 1 hour, allowing NaCl to react with Fe2O3 and the generated FeCl3 to volatilize; ③ Then, the heating furnace is cooled to room temperature, and the blocks are removed and soaked in water for a period of time to form the positive electrode.
[0035] The obtained cathode material is NaTiO2.
[0036] The electrolyte is prepared using polyaluminum trichloride and water, with polyaluminum trichloride accounting for 12%-15% of the total electrolyte weight.
[0037] The negative electrode uses a graphite cell, which contains electrolyte.
[0038] It should be noted that when the electrolyte in this battery is insufficient, an enhancement solution should be added after charging. The enhancement solution is prepared from sodium hypochlorite, sodium chloride, and water; wherein, sodium hypochlorite accounts for 15% of the total electrolyte weight and sodium chloride accounts for 7.5% of the total electrolyte weight.
[0039] (Example 4) This embodiment provides a sodium titanate battery, which has a positive electrode, a negative electrode, and an electrolyte.
[0040] The positive electrode A3 is prepared using 34.3 parts TiO2, 38.2 parts NaCl, and 27.5 parts Fe2O3. The preparation process is as follows: ① First, the powders of each material are mixed according to the weight ratio and pressed into blocks; ② Then, the blocks are placed in a corresponding heating furnace and heated to 315℃, then further heated to 1100℃ and held at that temperature for 1 hour, allowing NaCl to react with Fe2O3 and the generated FeCl3 to volatilize; ③ Then, the heating furnace is cooled to room temperature, and the blocks are removed and soaked in water for a period of time to form the positive electrode.
[0041] The obtained cathode material is Na2FeTi2O5.
[0042] The electrolyte is prepared using polyaluminum trichloride and water, with polyaluminum trichloride accounting for 12%-15% of the total electrolyte weight.
[0043] The negative electrode uses a graphite cell, which contains electrolyte.
[0044] It should be noted that when the electrolyte in this battery is insufficient, an enhancement solution should be added after charging. The enhancement solution is prepared from sodium hypochlorite, sodium chloride, and water; wherein, sodium hypochlorite accounts for 15% of the total electrolyte weight and sodium chloride accounts for 7.5% of the total electrolyte weight.
[0045] The reaction during discharge in this embodiment is as follows: .
[0046] The reaction in this embodiment during charging is as follows: .
[0047] (Test Example 1) I. The lowest voltage of the batteries in the above embodiments after being powered on (average data obtained after multiple measurements): 90V for Embodiment 1, 90V for Embodiment 2, 140V for Embodiment 3, and 140V for Embodiment 4.
[0048] II. Battery discharge performance test: (1) The voltage change after 12 hours of discharge in the above embodiment was tested, and the results are shown in the table below (average data obtained after multiple measurements): Unit: V (2) The current change after 12 hours of discharge in the above embodiment was tested, and the results are shown in the table below (average data obtained after multiple measurements): Unit: MA From the table above, we can obtain the discharge rate per unit of material: ① Sodium titanate: 38.1 MA / gs ②Sodium iron titanate A1: 45.6 MA / ms ③ Sodium titanate A2: 28.3 MA / ms ④ Sodium iron titanate A3: 23.6 MA / ms Therefore, this scheme has excellent discharge performance.
[0049] It should be noted that: 1. When charging, keep the DC output voltage of the charger between 30V and 60V for 4 hours; 2. Enhanced charging effect: After using up the electrolyte and charging, soaking the device in a sodium hypochlorite and sodium chloride solution for 3 hours every 3 days will improve the charging effect.
[0050] (Test Example 2) The voltage and current of the batteries prepared in Examples 1 to 4 were tested respectively, as follows: Figures 1-8 As shown: Figure 1 , Figure 2 The voltage and current conditions for Example 1 are as follows: voltage is 1.24V and current is 141.8mA; Figure 3 , Figure 4 The voltage and current conditions for Example 2 are as follows: voltage is 1.20V and current is 84.6mA; Figure 5 , Figure 6 The voltage and current conditions for Example 3 are as follows: voltage is 1.24V and current is 94.1mA; Figure 7 , Figure 8 The voltage and current conditions for Example 4 are as follows: voltage is 1.39V and current is 20.6mA.
[0051] It can be seen that in this scheme, when sodium titanate and sodium iron titanate are used as the positive electrode materials of the "conversion reaction" battery, the voltage is above 1V, which shows good electrical performance (significantly higher than 0.3V - which is the voltage of batteries using sodium titanate and sodium iron titanate as positive electrode materials).
[0052] The above embodiments only illustrate preferred implementation methods, and their descriptions are relatively specific and detailed, but they should not be construed as limiting the scope of this invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this invention, and these all fall within the protection scope of this invention.
Claims
1. A sodium titanate battery, characterized in that: It has a positive electrode, which is prepared from any of the following combinations of materials: The first type, by weight, includes 35.6 parts TiO2, 38.2 parts NaCl, and 26.2 parts ZnO; Alternatively, the second method, by weight, includes 25.6 parts TiO2, 38.2 parts NaCl, 10 parts Fe2O3, and 26.2 parts ZnO; Alternatively, the third type, by weight, includes 44.3 parts TiO2, 38.2 parts NaCl, and 17.5 parts Fe2O3; Alternatively, the fourth type, by weight, includes 34.3 parts TiO2, 38.2 parts NaCl, and 27.5 parts Fe2O3.
2. The sodium titanate battery according to claim 1, characterized in that: When preparing the positive electrode: If the first or second type is used as the positive electrode material, the powder of the corresponding material is mixed in a weight ratio and then pressed into a block. Then it is sent to the corresponding heating furnace and heated to 732°C and kept at that temperature for a period of time, and then heated to 1100°C and kept at that temperature for a period of time; Then let the heating furnace cool down to room temperature. After the corresponding block has cooled down, take it out and soak it in clean water for a period of time to form a positive electrode.
3. A sodium titanate battery according to claim 2, characterized in that: When preparing the positive electrode: it is placed in a heating furnace and heated to 732°C, then heated to 1100°C and kept at that temperature for 1 hour; after the cooled block is taken out, it is soaked in clean water for 0.5 hours.
4. A sodium titanate battery according to claim 1, characterized in that: When preparing the positive electrode: If the third or fourth type is used as the positive electrode material, the powder of the corresponding material is mixed in a weight ratio and then pressed into a block. Then it is sent to the corresponding heating furnace and heated to 315°C and kept at that temperature for a period of time, and then heated to 1100°C and kept at that temperature for a period of time. Then let the heating furnace cool down to room temperature. After the corresponding block has cooled down, take it out and soak it in clean water for a period of time to form a positive electrode.
5. A sodium titanate battery according to claim 4, characterized in that: When preparing the positive electrode: it is placed in a heating furnace and heated to 315°C, then heated to 1100°C and kept at a constant temperature for 1 hour; after the cooled block is taken out, it is soaked in clean water for 0.5 hours.
6. A sodium titanate battery according to any one of claims 1 to 5, characterized in that: It also contains an electrolyte, which is made of polyaluminum trichloride and water; wherein, polyaluminum trichloride accounts for 12%-15% of the total weight of the electrolyte.
7. A sodium titanate battery according to claim 6, characterized in that: When the electrolyte in the battery is insufficient, add an enhancing solution after charging. The enhancing solution is prepared from sodium hypochlorite, sodium chloride, and water; sodium hypochlorite accounts for 15% of the total electrolyte weight, and sodium chloride accounts for 7.5% of the total electrolyte weight.
8. A sodium titanate battery according to claim 7, characterized in that: It also has a negative electrode, which is a graphite tank containing electrolyte.