A method of activating a hydride battery

Abstract

The application discloses an activation method of a hydrogen negative ion battery, which comprises steps of low-temperature or room-temperature charging, programmed temperature charging, room-temperature charging and discharging cycling and the like. Similar to lithium batteries in large-scale commercial application, activation of hydrogen negative ion secondary batteries is also an indispensable step in the preparation process. The application has great practical value as an activation method of hydrogen negative ion batteries, which is favorable for optimizing the interface compatibility of electrode materials and electrolytes, and can improve the working voltage and the cyclic charging and discharging performance of the battery.

Description

TECHNICAL FIELD

[0001] The application relates to an activation method of a hydrogen negative ion battery, and belongs to the technical field of energy. BACKGROUND

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

[0003] The standard oxidation-reduction potential of hydrogen negative ion is-2.3V, close to that of magnesium ion (-2.4V), but the atomic mass is only 1 / 24 of that of magnesium, which makes it possible to be applied to a new generation of high-energy density and high-potential batteries, and to realize the innovation of electrochemical energy storage technology.

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

[0005] The application provides an activation method of a hydrogen negative ion battery. The appropriate activation step of the hydrogen negative ion is beneficial to improve the compatibility of the internal electrode and electrolyte interface of the hydrogen negative ion battery, optimize the ion transmission process, and improve the cycle charge and discharge performance.

[0006] According to one aspect of the application, an activation method of a hydrogen negative ion battery is provided, which comprises the following steps:

[0007] The hydrogen negative ion battery to be activated is subjected to constant current charging or discharging in sections to obtain an activated hydrogen negative ion battery.

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

[0009] (1) The first constant current charging stage: the hydrogen negative ion battery to be activated is charged with a constant current I at a temperature T1 for 20-600 minutes;

[0010] (2) The second constant current charging stage with temperature rise: the temperature is raised at a rate of 1-5℃ / min to a temperature T2, and the constant current II is used to continue constant current charging for 10-700 minutes;

[0011] (3) The third constant current charging stage with temperature drop: the temperature is lowered at a rate of 1-5℃ / min to a temperature T3, and the constant current III is used to continue constant current charging for 20-180 minutes;

[0012] (4) the fourth constant current constant voltage charging stage: charging to a preset voltage I cut-off at a T4 temperature using a constant current IV, and then continuing to charge to a current of 0.01C cut-off using a constant voltage A;

[0013] (5) the fifth constant current constant voltage discharging stage: discharging to a preset voltage II cut-off using a constant current V, and then continuing to discharge to a current of 0.01C cut-off using a constant voltage B;

[0014] (6) the sixth constant current constant voltage charging stage: charging to a preset voltage III cut-off using a constant current VI, and then continuing to charge to a current of 0.01C cut-off using a constant voltage C.

[0015] Optionally, the charge carrier ion conducted inside the hydrogen negative ion battery is a hydrogen negative ion (H - ).

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

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

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

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

[0020] Optionally, in the step (2), the T2 temperature is 50-250℃.

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

[0022] Optionally, in the step (3), the T3 temperature is 20-30℃.

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

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

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

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

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

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

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

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

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

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

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

[0034] Optionally, in the step (2), the temperature rising rate of the second temperature rising constant current charging stage is 1-5℃ / min.

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

[0036] Optionally, in the step (3), the temperature dropping rate of the third temperature dropping charging stage is 1-5℃ / min.

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

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

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

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

[0041] In the specific embodiments of the present application, the following technical solutions are implemented:

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

[0043] Step one, low temperature or room temperature constant current charging stage, set a constant current lower than 0.3C, the charging time is not less than 20 minutes; step two, temperature rising constant current charging stage, set a constant current lower than 0.3C, the charging time is not less than 20 minutes; step three, temperature decreasing charging stage, set a constant current lower than 0.2C, the charging process is accompanied by the whole temperature decreasing stage; step four, room temperature constant current constant voltage charging stage, the constant current is lower than 0.3C, constant current charging to the battery operating voltage to the preset voltage cutoff, then constant voltage charging to the current is 0.01C cutoff; step five, constant current constant voltage discharging stage, the constant current is lower than 1C, constant current discharging to the battery operating voltage to the preset voltage cutoff, then constant voltage discharging to the current is 0.01C cutoff; step six, constant current constant voltage charging stage, the constant current is lower than 1C, constant current charging to the battery operating voltage to the preset voltage cutoff, then constant voltage charging to the current is 0.01C cutoff.

[0044] The beneficial effects that can be produced by the present application include:

[0045] The hydrogen negative ion battery disclosed by the present application can operate at room temperature and higher temperature, and can realize multiple cycle charging and discharging. The new battery is expected to be applied to actual life and production.

[0046] The activation method for the hydrogen negative ion battery disclosed by the present application is beneficial to optimizing the interface compatibility of the electrode material and the electrolyte, can improve the working voltage and cycle charging and discharging performance of the hydrogen negative ion battery, and has great practical value. BRIEF DESCRIPTION OF DRAWINGS

[0047] Figure 1 It is a complete flow chart of the activation of the hydrogen negative ion battery in the embodiments 1-4 of the present application;

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

[0049] Figure 3 It is the constant current cycle charging and discharging curve of the cerium-based battery in the embodiment 2 of the present application at 40 microamperes before activation;

[0050] Figure 4 It is the constant current cycle charging and discharging curve of the cerium-based battery in the embodiment 2 of the present application at 40 microamperes after activation. DETAILED DESCRIPTION

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

[0052] Unless otherwise specified, the raw materials in the embodiments of the present application are purchased through commercial channels.

[0053] Embodiment 1 CeH2 / LaH xActivation method of a CeH3 battery, according to the scheme Figure 1 comprising the following steps:

[0054] Step S1, constant current charging phase at -40°C, current of 80 mA, charging time of 6 hours;

[0055] Step S2, temperature increasing constant current charging phase, temperature increase of 5°C / min to 80°C, current of 80 mA, charging time of 11 hours;

[0056] Step S3, temperature decreasing charging phase, temperature decrease of 2°C / min to 20°C, charging current constant at 80 mA, charging time of 30 minutes;

[0057] Step S4, room temperature constant current constant voltage charging phase, at 20°C, constant current of 80 mA, constant current charging to 450 mV, then constant voltage of 0.45 V charging to current of 0.01 C cut-off;

[0058] Step S5, constant current constant voltage discharging phase, constant current of 0.1 C, constant current discharging to 5 mV, then constant voltage of 0.005 V charging to current of 0.01 C cut-off;

[0059] Step S6, constant current constant voltage charging phase, constant current of 0.1 C, constant current charging to battery operating voltage to 370 mV, then constant voltage of 0.37 V charging to current of 0.01 C cut-off.

[0060] The constant current activation process of steps S1, S2, S3 is described in Figure 2 During the activation process, the voltage is gradually increased.

[0061] Example 2 CeH3 / CeH x Activation method of a CeH3 / CeH2 battery, based on the scheme Figure 1 Without step S1, the CeH3 / CeH2 battery is activated only by the following steps: x Activation of a CeH3 / CeH2 battery:

[0062] Step S2, temperature increasing constant current charging phase, temperature increase of 5°C / min to 120°C, current of 0.02 C, charging time of 32 minutes;

[0063] Step S3, temperature decreasing charging phase, temperature decrease of 2°C / min to 20°C, charging current constant at 0.02 C, charging time of 50 minutes;

[0064] Step S4, room temperature constant current constant voltage charging phase, at 20°C, constant current of 0.02 C, constant current charging to 400 mV, then constant voltage of 0.4 V charging to current of 0.01 C cut-off;

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

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

[0067] The cerium-based battery before activation was compared with the CeH3 / CeH3 activated in the above steps. x -BaH2 / CeH2 cerium-based batteries were compared using constant current charge-discharge cycles at 40 microamps, such as... Figure 3 As shown, unactivated CeH3 / CeH x -BaH2 / CeH2 batteries have a maximum voltage of only 0.11V, are difficult to discharge, have low capacity, and are difficult to charge and discharge multiple times. For example Figure 4 The activated CeH3 / CeH shown x -BaH2 / CeH2 batteries have improved cycle charge / discharge performance, increased capacity, and can reach a voltage of 0.38V.

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

[0069] Step S1: At 20°C, during the constant current charging stage, the current is 0.04C and the charging time is 40 minutes.

[0070] Step S2, constant current charging stage: the temperature is increased 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: Cool down to 20℃ at 3℃ / min, keep the charging current constant at 0.04C, and charge for 30 minutes.

[0072] Step S4, room temperature constant current and constant voltage charging stage: at 20℃, the constant current is 0.04C, and the constant current is charged to 500mV, and then the constant voltage is charged to 0.5V until the current is 0.01C cutoff.

[0073] Step S5, constant current and constant voltage discharge stage: constant current is 0.3C, constant current discharge to 5mV, then constant voltage discharge to 0.005V until current is 0.01C cutoff.

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

[0075] The activation method for constructing the LaNi5H6 / BaH2 / Pd battery of Example 4 comprises the following steps:

[0076] Step S1, constant current charging phase at -40℃, current is 0.02C, charging time is 50 minutes;

[0077] Step S2, temperature rising constant current charging phase, temperature rises to 120℃ at a rate of 5℃ / min, current is 0.02C, charging time is 32 minutes;

[0078] Step S3, temperature dropping charging phase, temperature drops to 20℃ at a rate of 2℃ / min, charging current is constant at 0.02C, charging time is 90 minutes;

[0079] Step S4, room temperature constant current constant voltage charging phase, constant current is 0.02C at 20℃, constant current charging to 1.5V, then constant voltage 1.5V charging to current is 0.01C cutoff;

[0080] Step S5, constant current constant voltage discharging phase, constant current is 0.1C, constant current discharging to 5mV, then constant voltage 0.005V discharging to current is 0.01C cutoff;

[0081] Step S6, constant current constant voltage charging phase, constant current is 0.1C, constant current charging to battery working voltage to 1.5V, then constant voltage 0.5V charging to current is 0.01C cutoff.

[0082] The above is only a few embodiments of the present application, and does not limit the present application in any form. Although the above describes the preferred embodiments of the present application, it is not intended to limit the present application. Any skilled person in the art can make some changes or modifications to the above disclosed technical content without departing from the scope of the technical solution of the present application, and such changes or modifications are equivalent to equivalent embodiments, which are within the scope of the technical solution.

Claims

1. A method of activating a hydride battery, characterized in that, The activation method comprises: The hydrogen negative ion battery to be activated is charged or discharged in segments to obtain the activated hydrogen negative ion battery; The activation method comprises the following steps: (1) first constant current charging stage: the hydrogen negative ion battery to be activated is charged with a constant current I at T1 temperature for 20-600 minutes; (2) second temperature-rising constant current charging stage: the temperature is raised at a temperature-rising rate of 1-5 ℃ / min to T2 temperature, and the charging is continued with a constant current II for 10-700 minutes; (3) third temperature-reducing charging stage: the temperature is reduced at a temperature-reducing rate of 1-5 ℃ / min to T3 temperature, and the charging is continued with a constant current III for 20-180 minutes; (4) fourth constant current and constant voltage charging stage: the charging is continued at T4 temperature with a constant current IV to a preset voltage I cut-off, and then with a constant voltage A to a current of 0.01C cut-off; (5) fifth constant current and constant voltage discharging stage: the discharging is continued with a constant current V to a preset voltage II cut-off, and then with a constant voltage B to a current of 0.01C cut-off; (6) sixth constant current and constant voltage charging stage: the charging is continued with a constant current VI to a preset voltage III cut-off, and then with a constant voltage C to a current of 0.01C cut-off.

2. The activation method of claim 1, wherein, In the step (1), the T1 temperature is -80-30 ℃. The constant current I is 0.02-0.3C.

3. The activation method of claim 1, wherein, In the step (1), the T1 temperature is -50-30 ℃.

4. The activation method of claim 1, wherein, In the step (2), the T2 temperature is 50-250 ℃. The constant current II is 0.02-0.3C.

5. The activation method of claim 1, wherein, In the step (3), the T3 temperature is 20-30 ℃. The constant current III is 0.01-0.2C.

6. The activation method of claim 1, wherein, In the step (4), the T4 temperature is 20-30 ℃. The constant current IV is 0.02-0.3C. The preset voltage I is 100-5000 mV. The constant voltage A is 0.1-5 V.

7. The activation method of claim 1, wherein, In the step (5), the constant current V is 0.1-1C. The preset voltage II is 0.001-500 mV. The constant voltage B is 0.001-0.5 V.

8. The activation method of claim 1, wherein, In the step (6), the constant current VI is 0.1-1C.

9. The method of activation of claim 2, wherein, In the step (6), the preset voltage III is 100-5000 mV.

10. The activation method of claim 1, wherein, In the step (6), the constant voltage C is 0.1-5 V.

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