CN112436133A - Wide-temperature nickel-metal hydride battery - Google Patents
Wide-temperature nickel-metal hydride battery Download PDFInfo
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- CN112436133A CN112436133A CN202011322542.2A CN202011322542A CN112436133A CN 112436133 A CN112436133 A CN 112436133A CN 202011322542 A CN202011322542 A CN 202011322542A CN 112436133 A CN112436133 A CN 112436133A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/383—Hydrogen absorbing alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/24—Alkaline accumulators
- H01M10/30—Nickel accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The wide-temperature nickel-metal hydride battery comprises a positive electrode and a negative electrode, wherein the negative electrode is made of negative electrode slurry, and the negative electrode slurry comprises the following raw materials in percentage by weight: 72.1 percent of A2B7 wide-temperature hydrogen storage alloy; 5.6 percent of nickel powder; 3.68% of a negative electrode additive; 2.34 percent of HPMC powder material 7.7 percent; 47% of SBR 0.94%; 10% of deionized water. The structural general formula of the A2B7 wide-temperature hydrogen storage alloy is as follows: laaMgbNicCodMneAlfWhere a is 0.9, b is 0.2, c is 6.5, d is 4, e is 2.5, and f is 0.4. The negative electrode additive is formed by uniformly mixing manganese dioxide, graphite fluoride and conductive graphite.
Description
Technical Field
The invention relates to the field of new energy, in particular to a wide-temperature nickel-metal hydride battery.
Background
Nickel-metal hydride batteries are new environmentally friendly batteries, and their development has received much attention in the battery industry. The negative electrode is an important component of the nickel-metal hydride battery, and the negative electrode of the nickel-metal hydride battery meets the high-performance requirement in order to enable the nickel-metal hydride battery to have the performances of good rate discharge performance, long cycle life, high specific capacity and the like.
Disclosure of Invention
In order to achieve the purpose, the invention adopts the following technical scheme:
the wide-temperature nickel-metal hydride battery comprises a positive electrode and a negative electrode, wherein the negative electrode is made of negative electrode slurry, and the negative electrode slurry comprises the following raw materials in percentage by weight: 72% -80% of A2B7 wide-temperature hydrogen storage alloy; 2.1 to 5.6 percent of nickel powder; 2.5% -3.68% of a negative electrode additive; 2.34 percent of HPMC powder material 3.32 percent to 7.7 percent; 47% of SBR 0.42% -0.94%; 10 to 15.6 percent of deionized water.
Preferably, the negative electrode slurry comprises the following raw materials in percentage by weight: 75.4% of A2B7 wide-temperature hydrogen storage alloy; 3.5 percent of nickel powder; 3.0% of a negative electrode additive; 2.34 percent of HPMC powder material 5 percent; 47% of SBR 0.75%; 12.35 percent of deionized water.
Preferably, the structural general formula of the A2B7 wide-temperature hydrogen storage alloy is as follows: laaMgbNicCodMneAlf，0.5 ≤a<2，0<b<1，3<c<10，5<d+e+f<9，0<e<3，0<f<1。
Preferably, the negative electrode additive is formed by uniformly mixing one or more of manganese dioxide, graphite fluoride and conductive graphite.
Preferably, the positive pole is made by the positive plate material, the positive plate material comprises positive plate body and outer covering, the positive plate body comprises ball-type nickel hydroxide, titanium dioxide and binder, the outer covering is the cobalt that the electrification covered in positive plate body surface.
Preferably, the cathode plate material comprises the following components in percentage by weight: 88 to 91 percent of spherical nickel hydroxide, 8 to 10 percent of cobalt, 0.5 to 3 percent of titanium dioxide and 0.5 to 1 percent of binder. In the technical scheme, the anode adopts electrochemical coating of 8-10% of Co and spherical nickel hydroxide, and titanium dioxide capable of improving high-temperature charging efficiency is added to serve as an anode material of the nickel-metal hydride battery; according to the selected nickel foam type polar plate structure, the polar plate has good mechanical strength and high conductivity by combining the positive active material with spherical nickel hydroxide with high energy density as a main component, cobalt, high-temperature additives and the like. In order to determine the proper plate current density, the unit active material filling amount is 235mAh/g after a plurality of tests. The surface of the positive plate material is covered with cobalt, so that the water loss is further reduced, and the oxygen evolution overpotential is reduced.
Preferably, the slurry mixing method of the negative electrode slurry is as follows:
a) sequentially pouring 2.345 percent of HPMC adhesive and negative electrode additive into a stirrer according to the proportion in a small amount and a plurality of times, stirring for 10min, adding deionized water, stirring for 10min, adding nickel powder, stirring for 30min, and checking the uniform stirring until no caking is formed;
b) weighing A2B7 wide-temperature hydrogen storage alloy according to the proportion, adding the alloy into a stirrer for stirring for multiple times, controlling the stirring speed to be 20 r/min-30 r/min at the beginning, then increasing the stirring speed, continuously stirring for 50min, then adding 47% SBR, stirring for 30min, checking and processing dry powder or slurry left on the bottom and the wall of a slurry barrel in time during stirring until the dry powder or slurry is uniformly stirred, and discharging the slurry without lumps and caking.
Has the advantages that:
1. charge-discharge efficiency: the charging and discharging efficiency of the nickel-metal hydride battery is 1.5 times higher than that of the current battery of the same type; 2C-4C heavy current charging and discharging are realized, the heavy current discharging duration is long, and the charging time can reach more than 90% of the rated capacity after being rapidly charged for 10-20 min; and the energy conversion rate is high, and the large-current energy circulation efficiency is more than or equal to 90 percent.
2. High-current discharge performance: the battery was discharged at 10ItA for 5s while charged, the cell casing was not deformed, there was no observable change in the internal components of the cell, and, in addition, there was no interruption in the cell voltage during discharge.
3. The discharge performance at the ambient temperature of 20 ℃, 5 ℃, 18 ℃ and 40 ℃ is shown in the following table;
in addition, under the condition of low temperature (-10 ℃) according to QB/T2947.2-2008 metal hydride nickel storage battery and charger for the second part of storage battery and charger for electric bicycle, the battery is charged according to the specification of 6.1.2.2.2, and then is placed in a low temperature box at-10 ℃ for 2 to 6 hours, and then 0.2I is added2(A) The current is discharged to the specified termination or battery protection, and the result is that the current meets the requirement of 5.1.2.3.2: i.e., its discharge capacity should not be less than 85% of the rated value. The product is 100.5% -103.0% in actual test data and far exceeds the existing standard.
At a high temperature (40 ℃), the battery was charged as specified above at 6.1.2.2.2, and the battery was left at 40 ℃The low temperature box is placed for 2 to 6 hours and then the temperature is controlled to be 0.2I2(A) The current is discharged to the specified termination or battery protection, and the result is that the current meets the requirement of 5.1.2.3.3: i.e., its discharge capacity should not be less than 95% of the rated value. The product is 109.5% -110.0% in actual test data, and is far beyond the existing standard. Therefore, the product can realize the normal use of the storage battery in high and low temperature states, and the actual charging and discharging efficiency of the storage battery is not influenced.
4. Charge acceptance capability
The storage battery is charged for 24 hours at a constant voltage of 1.455V +/-0.005V and with a current limit of 0.2ItA, and is discharged at a voltage of 0.2ItA after being placed for 1 hour, wherein the discharge time is more than or equal to 4 hours.
5. Charge retention capacity
The charged storage battery is discharged at 0.2ItA after being left open for 28 days, and the discharge time is more than or equal to 4 h.
6. Life span
According to the long cycle life, after 10000 times of cycle discharge test, the discharge capacity can still be maintained above 80% of the rated capacity, and after 20000 times of cycle discharge test, the discharge capacity can still be maintained above 60% of the rated capacity; under normal use and maintenance conditions, the design service life of the storage battery monomer is 12 years.
Detailed Description
The present invention will be further illustrated with reference to the following examples.
Example 1: the wide-temperature nickel-metal hydride battery comprises a positive electrode and a negative electrode, wherein the negative electrode is made of negative electrode slurry, and the negative electrode slurry comprises the following raw materials in percentage by weight: 72.1 percent of A2B7 wide-temperature hydrogen storage alloy; 5.6 percent of nickel powder; 3.68% of a negative electrode additive; 2.34 percent of HPMC powder material 7.7 percent; 47% of SBR 0.94%; 10% of deionized water. The structural general formula of the A2B7 wide-temperature hydrogen storage alloy is as follows: laaMgbNicCodMneAlfWhere a is 0.9, b is 0.2, c is 6.5, d is 4, e is 2.5, and f is 0.4. The negative electrode additive is formed by uniformly mixing manganese dioxide, graphite fluoride and conductive graphite.
Example 2: the wide-temperature nickel-metal hydride battery comprises a positive electrode and a negative electrode, wherein the negative electrode is made of negative electrode slurry, and the negative electrode slurry comprises the following raw materials in percentage by weight: the cathode slurry comprises the following raw materials in percentage by weight: 75.4% of A2B7 wide-temperature hydrogen storage alloy; 3.5 percent of nickel powder; 3.0% of conductive graphite; 2.34 percent of HPMC powder material 5 percent; 47% of SBR 0.75%; 12.35 percent of deionized water.
The structural general formula of the A2B7 wide-temperature hydrogen storage alloy is as follows: laaMgbNicCodMneAlfWhere a is 0.5, b is 0.6, c is 8.1, d is 6, e is 1.3, and f is 0.6.
The positive pole is made by the positive plate material, the positive plate material comprises positive plate body and outer covering, the positive plate body comprises ball-type nickel hydroxide, titanium dioxide and binder, the outer covering is the cobalt that the electrification covered in positive plate body surface. The anode plate material comprises the following components in percentage by weight: 88% of spherical nickel hydroxide, 10% of cobalt, 1.3% of titanium dioxide and 0.7% of binder. In the technical scheme, the anode adopts electrochemical coating of 10% Co and spherical nickel hydroxide, and titanium dioxide capable of improving high-temperature charging efficiency is added to serve as an anode material of the nickel-metal hydride battery; according to the selected nickel foam type polar plate structure, the polar plate has good mechanical strength and high conductivity by combining the positive active material with spherical nickel hydroxide with high energy density as a main component, cobalt, high-temperature additives and the like. In order to determine the proper plate current density, the unit active material filling amount is 235mAh/g after a plurality of tests. The surface of the positive plate material is covered with cobalt, so that the water loss is further reduced, and the oxygen evolution overpotential is reduced.
The slurry mixing method of the negative electrode slurry comprises the following steps:
a) sequentially pouring 2.345 percent of HPMC adhesive and negative electrode additive into a stirrer according to the proportion in a small amount and a plurality of times, stirring for 10min, adding deionized water, stirring for 10min, adding nickel powder, stirring for 30min, and checking the uniform stirring until no caking is formed;
b) weighing A2B7 wide-temperature hydrogen storage alloy according to the proportion, adding the alloy into a stirrer for stirring for multiple times, controlling the stirring speed to be 20 r/min-30 r/min at the beginning, then increasing the stirring speed, continuously stirring for 50min, then adding 47% SBR, stirring for 30min, checking and processing dry powder or slurry left on the bottom and the wall of a slurry barrel in time during stirring until the dry powder or slurry is uniformly stirred, and discharging the slurry without lumps and caking.
Through multiple tests, the relative mixture ratio of 2.34% HPMC powder, 47% SBR and deionized water in the A2B7 wide temperature type hydrogen storage alloy, nickel powder and the negative electrode additive has a large influence on the performance of the actual product, and the conventional A2B7 wide temperature type hydrogen storage alloy can also be adopted. The following experimental tests were carried out on 20 samples of example 2 according to the test method in QB/T2947.2-2008 "Nickel Metal hydride storage Battery and charger for electric bicycle" second part of Metal hydride storage Battery and charger therefor "; taking the average value or interval value.
The charging method as described below in this product refers strictly to the 6.1.2.2.2 charging system in the above regulation to obtain the most standard data. 6.1.2.2.2 charging system: the battery in the completely discharged state is firstly charged by 0.2I2(A) The current is charged to a charge termination voltage at a constant current, and the charging of the battery is stopped when the charge current is less than the termination/cutoff current during the constant voltage charging phase.
1. Charge-discharge efficiency: the charging and discharging efficiency of the nickel-metal hydride battery is 1.5 times higher than that of the current battery of the same type; 2C-4C heavy current charging and discharging are realized, the heavy current discharging duration is long, and the charging time can reach more than 90% of the rated capacity after being rapidly charged for 10-20 min; and has high energy conversion rate, large current energy circulation efficiency more than or equal to 90 percent,
2. high-current discharge performance: the battery was discharged at 10ItA for 5s while charged, the cell casing was not deformed, there was no observable change in the internal components of the cell, and, in addition, there was no interruption in the cell voltage during discharge.
3. The discharge performance at the ambient temperature of 20 ℃, 5 ℃, 18 ℃ and 40 ℃ is shown in the following table;
in addition, according to QB/T2947.2-2008, the second part of the metal hydride nickel storage battery and the charger for the electric bicycleBattery and charger thereof under low temperature (-10 deg.C), the battery is charged according to the above 6.1.2.2.2 rule, and then the battery is placed in a low temperature box at-10 deg.C for 2-6 h, and then 0.2I2(A) The current is discharged to the specified termination or battery protection, and the result is that the current meets the requirement of 5.1.2.3.2: i.e., its discharge capacity should not be less than 85% of the rated value. The product is 100.5% -103.0% in actual test data and far exceeds the existing standard.
Charging the battery at high temperature (40 deg.C) according to the above specification of 6.1.2.2.2, placing the battery in a low temperature box at 40 deg.C for 2-6 h, and standing at 0.2I2(A) The current is discharged to the specified termination or battery protection, and the result is that the current meets the requirement of 5.1.2.3.3: i.e., its discharge capacity should not be less than 95% of the rated value. The product is 109.5% -110.0% in actual test data, and is far beyond the existing standard. Therefore, the product can realize the normal use of the storage battery in high and low temperature states, and the actual charging and discharging efficiency of the storage battery is not influenced.
4. Charge acceptance capability
The storage battery is charged for 24 hours at a constant voltage of 1.455V +/-0.005V and with a current limit of 0.2ItA, and is discharged at a voltage of 0.2ItA after being placed for 1 hour, wherein the discharge time is more than or equal to 4 hours.
5. Charge retention capacity
The charged storage battery is discharged at 0.2ItA after being left open for 28 days, and the discharge time is more than or equal to 4 h.
According to QB/T2947.2-2008 "Nickel Metal hydride Battery and charger for electric bicycle" second part of Battery and charger thereof, the battery was charged according to the rule of 6.1.2.2.2, and then left for 30 days in open circuit mode, and then the battery was charged at 0.2I2(A) The current is discharged to a specified end voltage or battery protection, and the discharge capacity is calculated. The charge holding capacity is expressed by percentage of rated value, and the discharge capacity is not lower than 70% of rated value, and the product reaches 99.0% -102%.
6. Life span
According to the test method in QB/T2947.2-2008 "storage battery and charger for electric bicycle" metal hydride nickel storage battery and charger for second part ". The product is as described above6.1.2.2.2 charging regime in the regulations: the battery in the completely discharged state is firstly charged by 0.2I2(A) The current is charged to a charge termination voltage at a constant current, and the charging of the battery is stopped when the charge current is less than the termination/cutoff current during the constant voltage charging phase.
At 0.2I2(A) Discharging current to a specified end voltage or protecting the battery, continuously cycling under the specified condition of 6.1.2.2.1, wherein the intermittent switching time between charging and discharging does not exceed 60min, and stopping the test when the discharging capacity is continuously three times lower than 60% of the rated value (the three times do not count the cycle number). And recording the capacity and the frequency of the last discharge of the battery. The predetermined condition of 6.1.2.2.1 is an ambient temperature: 15-35 ℃; relative humidity: 25 to 85 percent; air pressure: the atmospheric pressure is 86kPa to 106 kPa.
According to the long cycle life, after 10000 times of cycle discharge test, the discharge capacity can still be maintained above 80% of the rated capacity, and after 20000 times of cycle discharge test, the discharge capacity can still be maintained above 60% of the rated capacity; under normal use and maintenance conditions, the design service life of the storage battery monomer is 12 years.
It should be understood that the above-described embodiments of the present invention are merely examples for illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. There is no need or no way to give poor examples of all embodiments. And such obvious changes and modifications which are within the spirit of the invention are deemed to be covered by the present invention.
Claims (7)
1. A wide temperature nickel-metal hydride battery is characterized in that: the cathode is made of cathode slurry, and the cathode slurry comprises the following raw materials in percentage by weight: 72% -80% of A2B7 wide-temperature hydrogen storage alloy; 2.1 to 5.6 percent of nickel powder; 2.5% -3.68% of a negative electrode additive; 2.34 percent of HPMC powder material 3.32 percent to 7.7 percent; 47% of SBR 0.42% -0.94%; 10 to 15.6 percent of deionized water.
2. The wide temperature nickel-metal hydride battery of claim 1, wherein: the cathode slurry comprises the following raw materials in percentage by weight: 75.4% of A2B7 wide-temperature hydrogen storage alloy; 3.5 percent of nickel powder; 3.0% of a negative electrode additive; 2.34 percent of HPMC powder material 5 percent; 47% of SBR 0.75%; 12.35 percent of deionized water.
3. The wide temperature nickel-metal hydride battery of claim 1, wherein: the structural general formula of the A2B7 wide-temperature hydrogen storage alloy is as follows: laaMgbNicCodMneAlf，0.5≤a<2，0<b<1，3<c<10，5<d+e+f<9，0<e<3，0<f<1。
4. The wide temperature nickel-metal hydride battery of claim 1, wherein: the negative electrode additive is formed by uniformly mixing one or more of manganese dioxide, graphite fluoride and conductive graphite.
5. The wide temperature nickel-metal hydride battery of claim 1, wherein: the positive pole is made by the positive plate material, the positive plate material comprises positive plate body and outer covering, the positive plate body comprises ball-type nickel hydroxide, titanium dioxide and binder, the outer covering is the cobalt that the electrification covered in positive plate body surface.
6. The wide temperature nickel-metal hydride battery as claimed in claim 5, wherein: the anode plate material comprises the following components in percentage by weight: 88 to 91 percent of spherical nickel hydroxide, 8 to 10 percent of cobalt, 0.5 to 3 percent of titanium dioxide and 0.5 to 1 percent of binder.
7. The wide-temperature nickel-metal hydride battery as claimed in claim 1, wherein the slurry mixing method of the negative electrode slurry is as follows:
a) sequentially pouring 2.345 percent of HPMC adhesive and negative electrode additive into a stirrer according to the proportion in a small amount and a plurality of times, stirring for 10min, adding deionized water, stirring for 10min, adding nickel powder, stirring for 30min, and checking the uniform stirring until no caking is formed;
b) weighing A2B7 wide-temperature hydrogen storage alloy according to the proportion, adding the alloy into a stirrer for stirring for multiple times, controlling the stirring speed to be 20 r/min-30 r/min at the beginning, then increasing the stirring speed, continuously stirring for 50min, then adding 47% SBR, stirring for 30min, checking and processing dry powder or slurry left on the bottom and the wall of a slurry barrel in time during stirring until the dry powder or slurry is uniformly stirred, and discharging the slurry without lumps and caking.
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