Activation method of hydrogen anion battery

Abstract

The invention discloses an activation method of a hydrogen negative ion battery. The activation method comprises the steps of a low-temperature or room-temperature charging process, a programmed heating charging process, room-temperature charging and discharging circulation and the like. Similar to a large-scale commercialized lithium battery, activation of a hydrogen negative ion secondary battery is also an essential step in the preparation process of the hydrogen negative ion secondary battery. The activation method for the hydrogen negative ion battery is beneficial to optimizing the interfacial compatibility of an electrode material and an electrolyte, can improve the working voltage and cyclic charge-discharge performance of the battery, and has great practical value.

Description

Technical Field

[0001] The present application relates to an activation method for a negative hydrogen ion battery, belonging to the field of energy technology. Background Art

[0002] Energy storage technology is an important part of human efficient use of energy and is of great significance. Secondary batteries have the advantages of high efficiency, safety, environmental protection, high energy storage density and high recycling rate, making them the only choice for energy storage devices. At present, secondary batteries have developed into lead-acid batteries, nickel-hydrogen batteries, lithium batteries, flow batteries, sodium batteries, magnesium batteries and other types.

[0003] The standard redox potential of hydrogen ions is -2.3V, close to that of magnesium ions (-2.4V), but their atomic mass is only 1 / 24 of that of magnesium. This makes them promising for use in a new generation of high-energy-density, high-potential batteries, thus revolutionizing electrochemical energy storage technology.

[0004] Similar to lithium batteries for large-scale commercial applications, activation of new negative hydrogen ion batteries is also an essential step in their preparation process. Summary of the invention

[0005] The present application provides a method for activating a negative hydride ion battery. Performing appropriate activation steps on negative hydride ions is beneficial to improving the compatibility of the internal electrode and electrolyte interface of the negative hydride ion battery, optimizing the ion transport process, and improving its cycle charge and discharge performance.

[0006] According to one aspect of the present application, a method for activating a negative hydride ion battery is provided, the activation method comprising the following steps:

[0007] The negative hydrogen ion battery to be activated is charged or discharged in sections with a constant current to obtain an activated negative hydrogen ion battery.

[0008] Optionally, the activation method comprises the following steps:

[0009] (1) First constant current charging stage: At temperature T1, the hydrogen anion battery to be activated is charged with a constant current I for 20 to 600 minutes;

[0010] (2) Second temperature rise constant current charging stage: the temperature is raised to T2 at a heating rate of 1 to 5°C / min, and constant current charging is continued for 10 to 700 minutes using constant current II;

[0011] (3) The third cooling charging stage: the temperature is lowered to T3 at a cooling rate of 1 to 5°C / min, during which constant current III is used to continue constant current charging for 20 to 180 minutes;

[0012] (4) Fourth constant current and constant voltage charging stage: At temperature T4, the charging is performed using a constant current IV until the preset voltage I is cut off, and then the charging is continued using a constant voltage A until the current reaches 0.01C and the charging is cut off;

[0013] (5) The fifth constant current and constant voltage discharge stage: the constant current V is used to discharge until the preset voltage II is cut off, and then the constant voltage B is used to discharge until the current is 0.01C and cut off;

[0014] (6) The sixth constant current and constant voltage charging stage: the battery is charged with a constant current VI until the preset voltage III is cut off, and then the battery is charged with a constant voltage C until the current reaches 0.01C and the battery is cut off.

[0015] Optionally, the load ions conducted inside the hydride ion battery are hydride ions (H - ).

[0016] Optionally, in step (1), the T1 temperature is -80 to 30°C.

[0017] Optionally, in step (1), the T1 temperature is selected from any value of -80°C, -50°C, -30°C, -10°C, 0°C, 10°C, 20°C, 30°C or a range between any two of the above.

[0018] Optionally, in step (1), the T1 temperature is -50 to 30°C.

[0019] Optionally, in step (1), the constant current I is 0.02-0.3C.

[0020] Optionally, in step (2), the T2 temperature is 50 to 250°C.

[0021] Optionally, in step (2), the constant current II is 0.02-0.3C.

[0022] Optionally, in step (3), the T3 temperature is 20 to 30°C.

[0023] Optionally, in step (3), the constant current III is 0.01-0.2C.

[0024] Optionally, in step (4), the T4 temperature is 20-30°C.

[0025] Optionally, the constant current IV is 0.02-0.3C.

[0026] Optionally, the preset voltage I is 100-5000 mV.

[0027] Optionally, the constant voltage A is 0.1-5V.

[0028] Optionally, in step (5), the constant current V is 0.1 to 1C.

[0029] Optionally, the preset voltage II is 0-500mV.

[0030] Optionally, the constant voltage B is 0.001-0.5V.

[0031] Optionally, in step (6), the constant current VI is 0.1 to 1C.

[0032] Optionally, in step (6), the preset voltage III is 100 to 5000 mV.

[0033] Optionally, in step (6), the constant voltage C is 0.1 to 5V.

[0034] Optionally, in step (2), the heating rate of the second temperature-raising constant-current charging stage is 1 to 5°C / min.

[0035] Optionally, the heating rate of the second temperature-rising constant-current charging stage is selected from any value of 1°C / min, 2°C / min, 3°C / min, 4°C / min, 5°C / min, or a range between any two of the above.

[0036] Optionally, in step (3), the cooling rate of the third cooling charging stage is 1 to 5°C / min.

[0037] Optionally, the cooling rate in the third cooling charging stage is selected from any value of 1°C / min, 2°C / min, 3°C / min, 4°C / min, 5°C / min, or a range between any two of the above.

[0038] Optionally, in step (4), the temperature of the fourth constant-current constant-voltage charging stage is 20-30°C.

[0039] Optionally, in step (5), the temperature is maintained at room temperature, and the cutoff voltage at the time of voltage cutoff should be based on the electrochemical properties of the positive and negative electrodes and should be higher than 0V.

[0040] Optionally, the negative hydrogen ion battery includes an all-solid-state battery or a non-all-solid-state battery.

[0041] In the specific implementation of this application, the following technical solutions are implemented:

[0042] The negative hydrogen ion battery activation method specifically comprises the following steps:

[0043] Step 1, low temperature or room temperature constant current charging stage, set the constant current lower than 0.3C, charging time is not less than 20 minutes; Step 2, temperature rise constant current charging stage, set the constant current lower than 0.3C, charging time is not less than 20 minutes; Step 3, cooling charging stage, set the constant current lower than 0.2C, the charging process accompanies the entire cooling stage; Step 4, room temperature constant current and constant voltage charging stage, the constant current is lower than 0.3C, constant current charging is performed until the battery working voltage reaches the preset voltage, and then constant voltage charging is performed until the current is 0.01C; Step 5, constant current and constant voltage discharge stage, the constant current is lower than 1C, constant current discharge is performed until the battery working voltage reaches the preset voltage, and then constant voltage discharge is performed until the current is 0.01C; Step 6, constant current and constant voltage charging stage, the constant current is lower than 1C, constant current charging is performed until the battery working voltage reaches the preset voltage, and then constant voltage charging is performed until the current is 0.01C.

[0044] The beneficial effects of this application include:

[0045] The negative hydrogen ion battery disclosed in the invention of this application can operate at room temperature and at higher temperatures, and can achieve multiple cycles of charge and discharge. This new type of battery is expected to be used in actual life and production.

[0046] The invention discloses an activation method for a negative hydrogen ion battery, which is beneficial to optimizing the interface compatibility between electrode materials and electrolytes, can improve the operating voltage and cycle charge and discharge performance of the negative hydrogen ion battery, and has great practical value. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] Figure 1 This is a complete flow chart of the activation of the negative hydrogen ion battery in Examples 1 to 4 of the present application;

[0048] Figure 2 This is the activation process of the lanthanum-based battery at 80 microamperes in Example 1 of the present application;

[0049] Figure 3 This is the constant current cycle charge and discharge curve of the cerium-based battery before activation at 40 microamperes in Example 2 of the present application;

[0050] Figure 4 This is the constant current cyclic charge and discharge curve of the activated cerium-based battery at 40 microamperes in Example 2 of the present application. DETAILED DESCRIPTION

[0051] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.

[0052] Unless otherwise specified, the raw materials in the examples of this application were purchased through commercial channels.

[0053] Example 1 CeH2 / LaH x / CeH3 battery activation method, according to the process Figure 1 , including the following steps:

[0054] Step S1, at -40°C, constant current charging stage, the current is 80 microamperes, and the charging time is 6 hours;

[0055] Step S2, temperature rising constant current charging stage, the temperature is raised to 80°C at 5°C / min, the current is 80 microamperes, and the charging time is 11 hours;

[0056] Step S3, cooling and charging stage, cooling to 20°C at 2°C / min, charging current constant at 80 μA, charging time 30 minutes;

[0057] Step S4, constant current and constant voltage charging stage at room temperature, at 20°C, the constant current is 80 microamperes, constant current charging to 450mV, then constant voltage 0.45V charging until the current reaches 0.01C and then cut off;

[0058] Step S5, constant current and constant voltage discharge stage, the constant current is 0.1C, constant current discharge to 5mV, then constant voltage 0.005V charging until the current is 0.01C and cut off;

[0059] Step S6, constant current and constant voltage charging stage, the constant current is 0.1C, constant current charging is performed until the battery operating voltage reaches 370mV, and then constant voltage charging is performed at 0.37V until the current reaches 0.01C and then the charging is stopped.

[0060] The constant current activation process of steps S1, S2, and S3 is shown in Figure 2 , during the activation process, the voltage gradually increases.

[0061] Example 2 CeH3 / CeH x -Activation method of BaH2 / CeH2 battery, based on process Figure 1 Without going through step S1, only the following steps are performed to treat CeH3 / CeH x -BaH2 / CeH2 battery activation:

[0062] Step S2, temperature rising constant current charging stage, the temperature is raised to 120°C at 5°C / min, the current is 0.02C, and the charging time is 32 minutes;

[0063] Step S3, cooling and charging stage, cooling to 20°C at 2°C / min, charging current constant at 0.02C, charging time 50 minutes;

[0064] Step S4, constant current and constant voltage charging stage at room temperature, at 20°C, the constant current is 0.02C, constant current charging to 400mV, then constant voltage charging at 0.4V until the current reaches 0.01C and then cut off;

[0065] Step S5, constant current and constant voltage discharge stage, the constant current is 0.1C, constant current discharge to 5mV, then constant voltage 0.005V discharge until the current is 0.01C and cut off;

[0066] Step S6, constant current and constant voltage charging stage, the constant current is 0.1C, constant current charging is performed until the battery operating voltage reaches 370mV, and then constant voltage charging is performed at 0.37V until the current reaches 0.01C and then the charging is stopped.

[0067] The cerium-based battery before activation and the CeH3 / CeH x -BaH2 / CeH2 cerium-based batteries were compared by constant current cyclic charge and discharge at 40 microamperes. Figure 3 As shown, the unactivated CeH3 / CeH x -The maximum voltage of BaH2 / CeH2 battery is only 0.11V, and it is difficult to discharge, has low capacity, and is difficult to achieve multiple charge and discharge. Figure 4 The CeH3 / CeH after activation is shown x -The cycle charge and discharge performance of BaH2 / CeH2 batteries is improved, the capacity is increased, and the voltage can reach 0.38V.

[0068] Example 3 Pd / PrH3-MgO / PdH 0.6 The battery activation method comprises the following steps:

[0069] Step S1, at 20°C, constant current charging stage, the current is 0.04C, and the charging time is 40 minutes;

[0070] Step S2, temperature rising and constant current charging stage, the temperature is raised to 120°C at 5°C / min, the current is 0.04C, and the charging time is 20 minutes;

[0071] Step S3, cooling and charging stage, cooling to 20°C at 3°C / min, charging current constant at 0.04C, charging time 30 minutes;

[0072] Step S4, constant current and constant voltage charging stage at room temperature, at 20°C, the constant current is 0.04C, constant current charging to 500mV, then constant voltage charging at 0.5V until the current reaches 0.01C and then cut off;

[0073] Step S5, constant current and constant voltage discharge stage, the constant current is 0.3C, constant current discharge to 5mV, then constant voltage 0.005V discharge until the current is 0.01C and cut off;

[0074] Step S6, constant current and constant voltage charging stage, the constant current is 0.3C, constant current charging is performed until the battery operating voltage reaches 450mV, and then constant voltage charging is performed at 450mV until the current reaches 0.01C and then the charging is stopped.

[0075] Example 4 A method for activating a LaNi5H6 / BaH2 / Pd battery is constructed, comprising the following steps:

[0076] Step S1, at -40°C, constant current charging stage, the current is 0.02C, and the charging time is 50 minutes;

[0077] Step S2, temperature rising and constant current charging stage, the temperature is raised to 120°C at 5°C / min, the current is 0.02C, and the charging time is 32 minutes;

[0078] Step S3, cooling and charging stage, cooling to 20°C at 2°C / min, charging current constant at 0.02C, charging time 90 minutes;

[0079] Step S4, constant current and constant voltage charging stage at room temperature, at 20°C, the constant current is 0.02C, constant current charging to 1.5V, then constant voltage 1.5V charging until the current reaches 0.01C and then cut off;

[0080] Step S5, constant current and constant voltage discharge stage, the constant current is 0.1C, constant current discharge to 5mV, then constant voltage 0.005V discharge until the current is 0.01C and cut off;

[0081] Step S6, constant current and constant voltage charging stage, the constant current is 0.1C, constant current charging is performed until the battery operating voltage reaches 1.5V, and then constant voltage charging is performed at 0.5V until the current reaches 0.01C and then the charging is stopped.

[0082] The above are only a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Any technician familiar with the profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A method for activating a negative hydrogen ion battery, characterized in that: The activation method comprises: The negative hydrogen ion battery to be activated is charged or discharged in sections with a constant current to obtain an activated negative hydrogen ion battery.

2. The activation method according to claim 1, characterized in that The activation method comprises the following steps: (1) First constant current charging stage: At temperature T1, the hydrogen anion battery to be activated is charged with a constant current I for 20 to 600 minutes; (2) Second temperature rise constant current charging stage: the temperature is raised to T2 at a heating rate of 1 to 5°C / min, and constant current charging is continued for 10 to 700 minutes using constant current II; (3) The third cooling charging stage: the temperature is lowered to T3 at a cooling rate of 1 to 5°C / min, and constant current charging is continued for 20 to 180 minutes using constant current III; (4) Fourth constant current and constant voltage charging stage: At temperature T4, the charging is performed using a constant current IV until the preset voltage I is cut off, and then the charging is continued using a constant voltage A until the current reaches 0.01C and the charging is cut off; (5) The fifth constant current and constant voltage discharge stage: the constant current V is used to discharge until the preset voltage II is cut off, and then the constant voltage B is used to discharge until the current is 0.01C and cut off; (6) The sixth constant current and constant voltage charging stage: the battery is charged with a constant current VI until the preset voltage III is cut off, and then the battery is charged with a constant voltage C until the current reaches 0.01C and the battery is cut off.

3. The activation method according to claim 2, characterized in that In the step (1), the temperature T1 is -80 to 30°C; Preferably, in step (1), the temperature T1 is -50 to 30°C; Preferably, in step (1), the constant current I is 0.02-0.3C.

4. The activation method according to claim 2, characterized in that In the step (2), the temperature T2 is 50 to 250°C; Preferably, in step (2), the constant current II is 0.02-0.3C.

5. The activation method according to claim 2, characterized in that: In the step (3), the temperature T3 is 20 to 30°C; Preferably, in step (3), the constant current III is 0.01-0.2C.

6. The activation method according to claim 2, characterized in that In the step (4), the temperature T4 is 20 to 30°C; Preferably, the constant current IV is 0.02-0.3C; Preferably, the preset voltage I is 100-5000mV; Preferably, the constant voltage A is 0.1-5V.

7. The activation method according to claim 2, characterized in that: In the step (5), the constant current V is 0.1 to 1C; Preferably, the preset voltage II is 0.001-500mV; Preferably, the constant voltage B is 0.001-0.5V.

8. The activation method according to claim 2, characterized in that: In the step (6), the constant current VI is 0.1 to 1C.

9. The activation method according to claim 2, characterized in that: In the step (6), the preset voltage III is 100 to 5000 mV.

10. The activation method according to claim 2, characterized in that: In the step (6), the constant voltage C is 0.1 to 5V.

Images