Classifications

• • 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
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C19/00—Alloys based on nickel or cobalt
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C30/00—Alloys containing less than 50% by weight of each constituent
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
• • 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

Definitions

• the invention belongs to the field of hydrogen storage materials and its application. Background technique
• Hydrogen storage alloys are a kind of high-density storage hydrogen functional materials discovered in the late 1960s. Hydrogen storage alloys can be roughly divided into six categories: rare earth AB 5 type such as LaNi 5 ; magnesium type such as Mg 2 Ni, MgN" La 2 Mg 17 ; rare earth - magnesium - nickel type AB 3 - 3 . 5 type such as La 2 MgNi 9 , La 5 Mg 2 Ni 23 , La 3 MgNi 14 ; titanium type AB such as TiNi, TiFe; zirconium Titanium Laves phase AB 2 type such as ZrNi 2 ; vanadium solid solution type such as ( Vo. J i o. ! !- x Fe x .
• rare earth AB 5 type such as LaNi 5
• magnesium type such as Mg 2 Ni, MgN" La 2 Mg 17
• rare earth - magnesium - nickel type AB 3 - 3 . 5 type such as La 2 MgNi 9 , La
• the hydrogen storage material is widely LaNi 5 type hydrogen storage alloy, a hydrogen storage capacity of about 1. 3 wt.%.
• the alloy is mainly used as a negative electrode material for metal hydride-nickel (MH/Ni) secondary batteries, and its theoretical electrochemical capacity is 373 mAh'g - a practical commercial anode material Mm (NiCoMnAl) 5 (where Mm is a mixed rare earth)
• the metal has a capacity of about 320 mAh.g - the hydrogen storage alloy has a high cost due to the high value of the metal element Co, and its dynamic performance and low temperature performance also need to be improved.
• the magnesium-based hydrogen storage alloy material has a high theoretical electrochemical capacity or a high hydrogen storage capacity, and is relatively inexpensive, but exhibits poor chemical stability due to the active metal element magnesium. Zirconium, titanium and vanadium hydrogen storage materials have not been widely used due to difficulties in activation and high cost.
• a Fe element may be substituted or a B element may be added.
• the reduction of cycling capacity degradation of Mg - Ni-based electrode alloys by Fe subs ti tut ion (International Journal of Hydrogen Energy) 27 (2002): 501-505 prepared Mg"Fe 5 Ni 5 by amorphous MA.
• the amorphous alloy has better cycle discharge capacity than the ternary alloy Mg 5 replaced by B side.
• the negative electrode active material of an alkaline nickel-hydrogen (MH-Ni) secondary battery and a metal hydride air (MH-Air) battery generally employs a rare earth-based AB 5 (LaNis) type hydrogen storage alloy.
• MH-Ni secondary batteries have the advantages of high specific energy, fast charge and discharge, no pollution and long life, and are widely used in portable wireless communication equipment and household appliances.
• High-power nickel-metal hydride batteries are also the main source of power for power tools, toys, and new energy vehicles such as hybrid electric vehicles (HEVs) and electric vehicles (EVs).
• MH metal hydride
• NiMH power batteries The main factors affecting the performance of NiMH power batteries include power performance, high/low temperature performance, cycle life, battery management systems, and more.
• the power performance of a nickel-hydrogen battery is required to enable the battery to discharge and charge at a high rate.
• the battery is generally charged at a current of 3C-10C, discharged at a current of 10C-30C, and the specific power at a depth of 50% reaches 1000W/Kg. To achieve such a level, it is necessary to improve from the selection of active materials (mainly hydrogen storage negative electrode alloys), overall battery design and manufacturing processes.
• active materials mainly hydrogen storage negative electrode alloys
• the invention patent discloses a surface treatment method of a LaNi 5 type negative electrode hydrogen storage alloy.
• the low temperature performance of the battery is mainly solved by improving the properties of the hydrogen storage alloy material.
• the use temperature of nickel-hydrogen batteries is generally in the range of -20 to 50, and is mainly used under the conditions of 0 to 40 Torr.
• nickel-metal hydride batteries can not meet the requirements of use, especially the nickel-hydrogen battery used in HEV and EV must ensure the cold start of the car in low temperature environment.
• NiMH batteries The cycle life of NiMH batteries is consistent with the life of the car, which is generally required to reach 8 years or 160,000 km.
• Nickel-metal hydride batteries for HEV applications are often used under conditions of shallow charge and shallow discharge of high-magnification or ultra-high-rate current.
• the termination condition of cycle life is not only the degree of capacity attenuation in general applications, but more importantly The attenuation of the power characteristics.
• the main reason for the decrease of the power characteristics of the nickel-hydrogen battery is the increase of the positive and negative resistances in the battery, and the increase of the positive resistance is nearly twice that of the negative electrode.
• the main reason is that the dissolution of the corrosion products of the negative electrode alloy, Al and Mn ions, reduces the specific surface area of the positive electrode. Accelerated low activity Y-NiOOH formation. Improving the corrosion resistance of the negative electrode alloy is an important way to improve the cycle life of the nickel-hydrogen battery.
• RE-Fe-B alloys have been studied as magnetic materials. Common chemical formulas include RE 2 Fe 14 B, RE 8 Fe 27 B 24 , RE 2 FeB 3 , RE 15 Fe 77 B 8 and the like. However, no RE-Fe-B alloy has been reported as a hydrogen storage material and its application. Many metals or alloys can absorb hydrogen more or less. The hydrogen-absorbing metal or alloy becomes brittle. This is the so-called "hydrogen embrittlement phenomenon". The "hydrogen embrittlement" of metal or alloy materials can be used to make powders, such as Nd. One of the powdering processes of the -Fe-B permanent magnet material is hydrogen embrittlement milling.
• a new hydrogen storage alloy was developed based on the chemical composition of the RE-Fe-B alloy.
• the RE-Fe-B alloy becomes a practical hydrogen storage material by replacing some or all of the elements such as RE, Fe, B and the like in the alloys with certain elements and corresponding preparation processes.
• the invented RE-Fe-B hydrogen storage alloy can be developed into a hydrogen storage material excellent in hydrogen storage and storage performance because it can contain inexpensive Fe element, B element with high chemical stability, and a unique multiphase structure.
• Developed into hydrogen storage materials with specific market requirements such as low-cost hydrogen storage materials, high-power wide-temperature hydrogen storage electrode alloys, low-temperature hydrogen storage alloys, low-self-discharge hydrogen storage materials, and high-temperature hydrogen storage materials.
• the inventive RE-Fe-B hydrogen storage alloy can be used for a negative electrode active material such as a nickel hydrogen battery or a metal hydride air battery, and can also be used for a vapor phase hydrogen absorption hydrogen storage material.
• the chemical composition of RE-Fe- B hydrogen storage alloy mainly includes RE 19 Fe 68 B 68 , RE Fe76B?, REisFe77Bs, REsFe2sB24, REsFeisBis-* RE 5 Fe 2 B 6 , RE 2 Fe 23 B 3 , RE 2 FeB 3 , RE 2 Fe"B.
• RE may be rare earth elements La (La ), ⁇ ( Ce ), ⁇ (Pr), ⁇ (Nd), ⁇ (Sm), ⁇ (Eu), ⁇ (Gd), ⁇ (Tb), ⁇ (Dy)
• RE can be chemical element
• Fe (iron) can be chemically periodicated Transition metal elements such as nickel (Ni), manganese (Mn), aluminum (A1), cobalt (Co), copper (Cu), zirconium (Zr), titanium (Ti), vanadium (V:), zinc (Zn) ,
• the atomic ratio of each element in the composition of the RE-Fe-B hydrogen storage alloy can be adjusted within a range of 20%.
• Nd 8 Fe 27 B 24 alloy can adjust the atomic ratio range of 6-10: 22-31: 20-28.
• the RE-Fe-B hydrogen storage alloy is a multi-phase structure including one or two or three of a LaNi 5 phase and a La 3 Ni 13 B 2 phase, a (Fe, Ni) phase, and a Ni phase, Other phase structures can also be formed by the difference in the substitution elements in the composition.
• the raw material for the production of the RE-Fe-B hydrogen storage alloy is a simple substance of RE (rare earth) and its substitute elements, a simple substance of Fe and its substitute elements, a simple substance of B and its substitute elements, and a RE-Fe alloy. , B-Fe alloy, B-Ni alloy, RE-Ni alloy, RE-Fe-B alloy and other intermediate alloys containing constituent elements. Two or more kinds of raw materials are prepared according to the chemical composition formula of the alloy.
• the RE-Fe-B hydrogen storage alloy can be improved in structure and properties by one of the following heat treatment methods.
• the high-temperature smelted RE-Fe-B hydrogen storage alloy is subjected to a stage heat treatment in an environment of a vacuum of 10 - 2 - 10 - 6 Pa or in an inert gas atmosphere.
• the alloy is first heated to 850-1050 C for 2-6 hours, then held at 450-850 for 2-6 hours, and the hydrogen storage alloy after cooling is cooled to room temperature with the furnace.
• the RE-Fe-B hydrogen storage alloy is prepared by a jet mill or a ball mill or a hammer mill or a high temperature atomization method to prepare particles or powder having a particle size of 0.3 to 10 legs.
• the RE-Fe-B hydrogen storage alloy particles or powder may be subjected to surface treatment by physical, chemical or mechanical means to improve the properties thereof.
• the present invention also provides a nickel-hydrogen secondary battery and a metal hydride air (MH-Ai r ) battery comprising the RE-Fe-B hydrogen storage electrode alloy, the battery comprising a positive electrode, a separator, a negative electrode and an electrolyte. They are packaged in a battery case.
• the negative electrode active material of the nickel-hydrogen secondary battery and the metal hydride air battery is the RE-Fe-B-based hydrogen storage alloy.
• the invention also provides a hydrogen storage and transportation device using the RE-Fe-B hydrogen storage alloy, which can be used for preparation and purification of fuel cells, heat pumps, hydrogen and its isotopes. It is characterized in that the hydrogen storage material in the hydrogen storage and transportation device is the RE-Fe-B hydrogen storage alloy.
• the RE-Fe-B hydrogen storage alloy of the present invention is a novel hydrogen storage alloy having a composition and structure different from that of the existing hydrogen storage alloy.
• the new alloy has lower cost, good high current discharge characteristics and low temperature discharge characteristics. Effect of the invention
• the hydrogen storage alloy of the RE-Fe-B hydrogen storage alloy of the present invention has a hydrogen storage capacity of more than 1. 0 wt. %; the hydrogen storage alloy electrode has good activation performance, and the discharge capacity is generally greater than 300 mAh-g- 1 ; The hydrogen storage alloy electrode has excellent high current discharge capability and good dynamic performance.
• the charging efficiency of 3C (0.9 A/g) -10C (3A/g) is over 90%, and the discharge time of 30C (10A/g) is greater than 15 s ;
• the hydrogen storage alloy electrode has good low temperature discharge performance, - 40 X discharge capacity is greater than 50% of the rated capacity;
• the hydrogen storage alloy has good corrosion resistance and small suction and discharge due to the unique composition and structure Hydrogen expansion rate, thus having good charge and discharge or hydrogen absorption and desorption cycle stability.
• the hydrogen absorbing alloy can be produced by using an inexpensive raw material such as Fe and a material having a higher value such as Co, and thus having a lower cost.
• the hydrogen storage alloy of the present invention can be used to manufacture a battery comprising a metal hydride (MH) electrode and a hydrogen storage and transportation device comprising a hydrogen storage alloy.
• RE is La and Ce, Pr, Nd
• Ni, Mn, and A1 are used to partially replace Fe and B.
• the alloy compositions prepared are Lai 5 Fei2Ni64Mn 5 B2Al 2 , Lan.5?Cei. nPr 0 . 3 4Nd 0 . 98 Fei 2 N i 6 oMn 5 B 4 A 1 4 , La 8 Fe 4 Ni 35 Mii 5 B 5 Al3 , La . i 9 Ce 0 .37 ⁇ ⁇ 0. nNd 0 .
• the constituent elements are calculated and weighed (the purity is greater than 99.0%, and the B element can be B-Fe or B-
• the form of the Ni alloy is added as a raw material for preparing the alloy.
• the medium-frequency induction melting process is used to prepare the alloy by high-temperature melting under the protection of Ar gas.
• the test electrode is prepared by mechanically breaking the alloy into a powder of 50-150 ⁇ , mixing the alloy powder with the nickel carbonyl powder in a mass ratio of 1:4, and forming a ⁇ 15 female electrode sheet under a pressure of 16 MPa, the electrode sheet Placed between two pieces of foamed nickel, while sandwiching the nickel strip as a tab, and again making a hydrogen storage negative electrode (MH electrode) for testing under the pressure of 16 MPa, and ensuring the electrode sheet and nickel by spot welding around the electrode sheet. Close contact between the nets.
• MH electrode hydrogen storage negative electrode
• the negative electrode in the open-ended two-electrode system for testing electrochemical performance is the MH electrode, the positive electrode is used for the sintered Ni (0H) 2 /Ni00H electrode with excess capacity, the electrolyte is 6 mol'L - 1 K0H solution, and the assembled battery is placed on hold. 24 h, using LAND battery tester to determine the electrochemical performance of the alloy electrode by the galvanostatic method (activation number, maximum capacity, high rate discharge capacity HRD, cycle stability, etc.), test ambient temperature is 25, charging current density 70 mA- G- 1 , charging time 6 h, discharge current density 70 mA-g" 1 , discharge cut-off potential is 1.0 V, charge/discharge intermittent time 10 min. Test results are shown in Table 1. Table 1 RE-Fe-B system Electrochemical characteristics of alloy electrodes
• a is the number of cycles required for electrode activation; b is the maximum discharge capacity; c is The capacity retention rate of 100 cycles; d is the rate discharge capability when the discharge current density Id is 350 mA'g- 1 .
• Example 2 is the number of cycles required for electrode activation; b is the maximum discharge capacity; c is The capacity retention rate of 100 cycles; d is the rate discharge capability when the discharge current density Id is 350 mA'g- 1 .
• the alloy compositions prepared are respectively La 8 Fe 4 Ni 34 Mn 5 B 5 Al 3 , La 15 Fe 7 Ni 65 Mn 5 B 4 Al 4 and La 17 Fe 6 Ni 65 Mn 5 B 4 Al 3 .
• the medium-frequency induction melting-quick quenching process is used to form the RE-Fe-B alloy flakes under the protection of Ar gas.
• the prepared alloy flakes are subjected to heat treatment under vacuum or inert gas treatment under the conditions of: 850-1050 Torr for 2-5 hours, and then incubated at 450-850 for 2-5 hours.
• the microstructure of the alloy was analyzed by Phi 1 ips-PW1700 X-ray diffractometer.
• the alloy was a multiphase structure dominated by LaNi 5 phase, including LaNi 5 phase, La 3 Ni 13 B 2 phase, (Fe, Ni ) phase. And Ni phase.
• Figure 1 and Figure 2 are XRD patterns of the rapidly quenched and annealed states of La 15 Fe 7 Ni 65 Mn 5 B 4 Al 4 alloy, respectively.
• the pressure-composition isotherm curve of the alloy was measured at 313 K using the Sievert method. The results show that the alloy has very good reversible hydrogen absorption and desorption characteristics, the platform pressure is between 0.01-0.10 MPa, and the hydrogen storage capacity of the alloy is greater than 1.0 wt.%.
• 3, 4 and 5 are the -c- ⁇ curves of the annealed state of the RE 8 Fe 27 B 24 , La 15 Fe 77 B 8 and RE 17 Fe 76 B 7 alloys, respectively.
• the prepared alloy composition is RE 19 (FeNiMn ) 68 ( BMnAl ) 68 , RE 17 (FeNiMn ) 76 ( ⁇ 1 ) 7, RE 15 (FeNiMn ) 77 (BMnAl ) 8 , RE 15 (FeNiMnCu ) 77 ( BMnAl ) 8 , RE 15 (FeNiMnCu) 77 (BMnAISi ) 8 , RE 8 (FeNiMn) 86 (BMnAl ) 6 , RE 8 (FeNiMn) 27 (BMnAl ) 24 , RE 5 ( FeNiMn ) 18 ( BMnAl ) 18 , RE 5 ( FeNiMn ) 2 (BMnAl) 6 , RE 2 (FeNiMn ) 23 ( BMnAl ) 3 , RE 2 (FeNiMn ) ( BMnAl ) 3 , RE 2 (F
• the alloy preparation and heat treatment method was the same as in Example 2.
• the preparation method of the test electrode and the battery assembly and test method were the same as those in Example 1. The results of some alloy tests in the examples are shown in Table 2.
• the alloy composition prepared was RE 15 (FeNiMn) 77 (BMnAl ) 8 .
• the elemental metal La, metal Ni, metal Mn, metal A1, and La-Fe, B-Fe alloy are used as raw materials, and La and Mn are considered.
• the smelting of the A1 element is burned, and various raw materials are calculated and weighed (purity is greater than 99.0%). They are prepared by high-temperature smelting casting method, high-temperature smelting-gas atomization method, and powder sintering method, respectively.
• the preparation process was carried out under the protection of Ar gas.
• the preparation method of the test electrode and the battery assembly and test method were the same as those in Example 1. The test results are shown in Table 3. Table 3 Comparison of different preparation methods of RE 15 (FeNiMn) "(BMnAl) 8 hydrogen storage alloy
• the alloy composition is RE 19 (FeNiMn) 6g ( BMnAl ) 68 , RE delete (FeNiMn) 76 ( BMnAl ) 7 , RE 15 ( FeNiMn ) 77 ( BMnAl ) 8 , RE 15 ( FeNiMnCu ) 77 ( BMnAl ) 8 , RE 15 ( FeNiMnCu) " (BMnAISi) 8 , RE 8 (FeNiMn) 86 (BMnAl ) 6 , RE 8 (FeNiMn ) 27 (BMnAl ) 24 , RE 5 ( FeNiMn ) 18 ( BMnAl ) 18 , RE 5 ( FeNiMn ) 2 ( BMnAl ) 6.
• the medium-frequency induction melting-quick quenching process is used to make RE-Fe-B alloy flakes under the protection of Ar gas.
• the prepared alloy flakes were subjected to heat treatment in a vacuum degree of 1 (T 2 Pa) under heat treatment conditions of: 950 for 3 hours, then at 600 t; for 3 hours, and the heat-storing alloy after cooling was cooled to room temperature with the furnace.
• the preparation method of the test electrode and the battery assembly and test method were the same as those in Example 1. The test results are shown in Table 4.
• the prepared RE 15 (FeNiMn) " ( BMnAl ) 8 hydrogen storage alloy sheet was sealed in two quartz glass tubes with a vacuum of 10 _ 2 Pa.
• the quartz glass tube with the alloy flakes was placed in a heat treatment furnace for heating and holding.
• the heat treatment condition is 950 for 5 hours.
• the quartz glass tube with the alloy flakes is immediately taken out, one is placed in the water, the other is placed in the oil, and the glass tube is broken, so that the alloy flakes are Quenching medium contact, quenching treatment.
• Electrode preparation and electrochemical performance test method Same as Example 1. The test results are shown in Table 5. Table 5 Comparison of performance of RE 15 (FeNiMn ) 77 ( BMnAl ) 8 hydrogen storage alloy in different quenching media
• RE is a rare earth element, and Ni Mn Al Cu is used.
• the element partially replaces the Fe B element, and the prepared alloy composition is listed in Table 6.
• the alloy preparation and heat treatment method is the same as in Example 5.
• the test electrode preparation method and the battery assembly and test method are the same as those in the first embodiment.
• the charging efficiency of the prepared alloy electrode 3C (0.9 A/g) -10C (3A/g) (0.
• the ratio of the discharge capacity of 2C to the rated capacity) is more than 90%, and the capacity retention rate of the charge and discharge cycle is more than 80%.
• the test results of other properties are shown in Table 6.
• a is the number of cycles required for electrode activation; b is the maximum discharge capacity; c is the discharge current density Id is 10C; the rate discharge capacity at 20C; d is the discharge current density Id The discharge time at 30C; e is the ratio of the discharge capacity to the rated capacity of -40.
• Example 8 is the ratio of the discharge capacity to the rated capacity of -40.
• RE is a rare earth element
• Ni is used.
• the Mn, Al, and Cu elements partially replace the Fe and B elements, and the alloy composition prepared is as listed in Table 10.
• the alloy preparation and heat treatment method was the same as in Example 5.
• the preparation method of the test electrode and the battery assembly and test method were the same as those in Example 1.
• the capacity retention rate of the charge and discharge cycle of 500 times was 80% or more.
• the test results of other properties are shown in Table 7. Table 7 Low-temperature discharge characteristics of RE-Fe-B alloy electrodes
• La6Ce2FesNi «MnB 3 301 63 95 86 74 La6Sm2Fe5Ni 4MnB 3 290 67 98 90 81
• a is the number of cycles required for electrode activation
• b is the maximum discharge capacity
• c is the rate discharge capacity when the discharge current density Id is 10C (3A/g)
• d is the ambient temperature respectively *C, - 30"C, the ratio of discharge capacity to rated capacity.

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