WO2020006839A1

WO2020006839A1 - Zinc borohydride hydrogen storage material

Info

Publication number: WO2020006839A1
Application number: PCT/CN2018/102075
Authority: WO
Inventors: 黄倩
Original assignee: 黄倩
Priority date: 2018-07-03
Filing date: 2018-08-24
Publication date: 2020-01-09
Also published as: CN108793069A

Abstract

The present application relates to the field of new energy materials and discloses a zinc borohydride hydrogen storage material, which is prepared by the following method: providing a raw material powder of NaBH₄ and ZnCl₂; subjecting the raw material powder of NaBH₄ and ZnCl₂ to a first ball milling to obtain a primary zinc borohydride powder; subjecting the primary zinc borohydride powder to a first heat treatment; providing a metal powder of Ti, Al, Ni and Cu; mixing the metal powder of Ti, Al, Ni and Cu and the heat treated primary zinc borohydride powder to obtain a first mixed powder; subjecting the first mixed powder to a second ball milling to obtain a second mixed powder; subjecting the second mixed powder to a second heat treatment to obtain a third mixed powder; subjecting the third mixed powder to a third ball milling to obtain a fourth mixed powder; and subjecting the fourth mixed powder to a third heat treatment. The zinc borohydride hydrogen storage material has a high hydrogen storage capacity and good stability during cyclical hydrogen storage.

Description

Zinc borohydride series hydrogen storage material

Technical field

The invention relates to the technical field of new energy materials, in particular to a zinc borohydride series hydrogen storage material.

Background technique

Solid material hydrogen storage is a hydrogen storage technology that uses hydrogen absorbing materials to react with hydrogen to form solid solutions and hydrides. In this method, hydrogen is generally stored in the form of atoms or ions in the material. The re-release of hydrogen needs to go through stages such as diffusion, phase transition, and compounding. The period is mainly affected by thermal effects and speed. Compared with traditional high-pressure cylinder hydrogen storage and low-temperature liquefied hydrogen storage, solid material hydrogen storage has the characteristics of good safety, low cost, and high hydrogen storage density. It is especially suitable for occasions with strict space and volume requirements, such as vehicle fuel cells. Application. Therefore, countries around the world have conducted a lot of research on hydrogen storage in solid materials, and have developed rapidly in recent years. At present, solid-state hydrogen storage technologies mainly include metal hydride hydrogen storage, new carbon-based material hydrogen storage, metal-organic framework hydrogen storage, metal nitrogen-hydrogen-based material storage, and complex hydride hydrogen storage. The mechanism of metal hydride hydrogen storage is that the hydrogen atoms enter the tetrahedral or octahedral gap of the metal lattice to form the metal hydride. When the hydrogen storage material is heated to a certain temperature, it can release hydrogen again, and utilize this characteristic to realize the storage of hydrogen. Traditional metal hydride hydrogen storage materials can be divided into rare earth-based hydrogen storage alloys, titanium-based hydrogen storage alloys, magnesium-based hydrogen storage alloys, zirconium-based hydrogen storage alloys, and vanadium-based solid solution-type hydrogen storage alloys. Representative metal hydrides include LaNi5 and TiFe hydrogen storage alloys. Although metal hydrides have advantages such as high volume hydrogen storage density and safety, but their effective mass hydrogen storage density is mostly less than 3% by weight, which cannot meet the requirements of vehicle fuel cells for their hydrogen storage system quality hydrogen storage density. In addition, metal hydrides also need to absorb heat from the outside when dehydrogenating, which results in higher hydrogen storage costs.

The information disclosed in this Background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that the information constitutes prior art that is already known to a person of ordinary skill in the art.

Summary of the invention

The purpose of the present invention is to provide a zinc borohydride-based hydrogen storage material, thereby overcoming the disadvantages of the prior art.

To achieve the above object, the present invention provides a zinc borohydride-based hydrogen storage material, wherein: zinc borohydride-based hydrogen storage material is prepared by the following process: providing NaBH ₄ and ZnCl ₂ raw material powder; of NaBH ₄ and ZnCl ₂ raw material powder is subjected to the first ball milling to obtain a primary zinc borohydride powder; the primary zinc borohydride powder is subjected to a first heat treatment; Ti, Al, Ni, and Cu metal powders are provided; Ti, Al, Ni, and Cu metal powders and heat treatment are provided The subsequent primary zinc borohydride powder is mixed to obtain a first mixed powder; a second ball milling is performed on the first mixed powder to obtain a second mixed powder; a second heat treatment is performed on the second mixed powder to obtain a third mixed powder; The mixed powder is subjected to a third ball milling to obtain a fourth mixed powder; the fourth mixed powder is subjected to a third heat treatment.

Preferably, in the above technical solution, the first ball milling of the NaBH ₄ and ZnCl ₂ raw material powder is specifically: the ball-to-material ratio is 5: 1-7: 1, the ball milling atmosphere is an argon atmosphere, and the ball milling speed is 500-600r / min The ball milling time is 150-180min. In the ball milling process, each ball milling is 10-15min, the ball milling is suspended for 2-4min. During the ball milling process, the temperature in the ball milling tank is controlled below 200 ° C.

Preferably, in the above technical solution, the first heat treatment of the primary zinc borohydride powder is specifically: the heat treatment atmosphere is a hydrogen atmosphere, the heat treatment temperature is 200-250 ° C, the heat treatment time is 5-10min, and the heating rate is 30-40 ° C min.

Preferably, in the above technical solution, in the first mixed powder, the primary zinc borohydride powder after heat treatment accounts for 100-120 parts, the Ti metal powder accounts for 3-5 parts, and the Al metal powder accounts for 2-4 parts by weight. Parts, Ni metal powder accounts for 1-3 parts, and Cu metal powder accounts for 8-10 parts.

Preferably, in the above technical solution, the second ball milling of the first mixed powder is specifically: the ball-to-material ratio is 8: 1-10: 1, the ball milling atmosphere is an argon atmosphere, the ball milling speed is 700-800r / min, and the ball milling time is It is 80-100min, during the ball milling process, each ball is milled for 10-15min, and the ball milling is suspended for 2-4min. During the ball milling process, the temperature in the ball mill tank is controlled below 200 ° C.

Preferably, in the above technical solution, the second heat treatment of the second mixed powder is specifically: the heat treatment atmosphere is a hydrogen atmosphere, the heat treatment temperature is 180-220 ° C, the heat treatment time is 4-8min, and the heating rate is 30-40 ° C / min .

Preferably, in the above technical solution, the third ball milling of the third mixed powder is specifically: the ball-to-material ratio is 10: 1-12: 1, the ball milling atmosphere is an argon atmosphere, the ball milling speed is 850-1000r / min, and the ball milling time It is 100-150min, during the ball milling process, each ball milling is 5-10min, and the ball milling is suspended for 2-4min. During the ball milling process, the temperature in the ball milling tank is controlled below 200 ° C.

Preferably, in the above technical solution, the third heat treatment for the fourth mixed powder is specifically: the heat treatment atmosphere is a hydrogen atmosphere, the heat treatment temperature is 160-200 ° C, the heat treatment time is 4-8min, and the heating rate is 30-40 ° C / min .

Compared with the prior art, the present invention has the following beneficial effects: zinc borohydride belongs to a complex hydride hydrogen storage material. In the prior art, many studies have been conducted on coordinated hydride hydrogen storage materials, and components of various coordinated hydride hydrogen storage materials and their preparation methods have also been disclosed. However, these existing technologies have some shortcomings. First of all, the current methods for preparing coordination hydride hydrogen storage materials designed in the prior art belong to the preparation methods and processes in the laboratory. Such preparation methods and processes generally require strict control. The process reaction conditions, reaction speed, and also put high requirements on the operator, and this type of laboratory process does not require yield. This preparation method does not actually have practical guiding significance for industrial production. How to realize industrialized production of complex hydride hydrogen storage materials has become a problem in the prior art. Aiming at the problems of the prior art, the present invention proposes a method for preparing a coordinated hydride hydrogen storage material that can be applied to industrial production. Although the method of the present application has many process steps, the present invention requires operation requirements for these process steps and The numerical deviation requirements are not high. For example, in the heating process, temperature overshoot is an inevitable problem. The tolerance for temperature overshoot in this application can reach 50-80 ° C. This greatly reduces the difficulty of temperature control and achieves rapid heating, which saves production time. At the same time, the zinc borohydride material prepared by the method of the present invention has strong hydrogen storage capacity, good stability of cyclic hydrogen storage, and its basic performance can be equal to the laboratory-grade zinc borohydride in the prior art or due to the existing technology.

detailed description

Hereinafter, exemplary embodiments of the present disclosure will be described in more detail with reference to the accompanying drawings. Although exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure can be implemented in various forms and should not be limited by the embodiments set forth herein. On the contrary, these embodiments are provided to enable a thorough understanding of the present disclosure, and to fully convey the scope of the present disclosure to those skilled in the art.

Example 1

The zinc borohydride-based hydrogen storage material is prepared by providing: NaBH ₄ and ZnCl ₂ raw material powders; first ball milling the NaBH ₄ and ZnCl ₂ raw material powders to obtain primary zinc borohydride powder; First heat treatment; providing Ti, Al, Ni, and Cu metal powders; mixing Ti, Al, Ni, and Cu metal powders and primary zinc borohydride powders after heat treatment to obtain a first mixed powder; Ball milling to obtain a second mixed powder; second heat treatment of the second mixed powder to obtain a third mixed powder; third ball milling of the third mixed powder to obtain a fourth mixed powder; and third heat treatment to the fourth mixed powder. The first ball milling of NaBH ₄ and ZnCl ₂ raw material powder is specifically: the ball-to-material ratio is 5: 1, the ball milling atmosphere is an argon atmosphere, the ball milling speed is 500 r / min, the ball milling time is 150 minutes, and each ball milling during the ball milling process is 10 minutes, Pause the ball mill for 2 minutes, and control the temperature in the ball mill tank below 200 ° C during the ball mill. The first heat treatment of the primary zinc borohydride powder is specifically: the heat treatment atmosphere is a hydrogen atmosphere, the heat treatment temperature is 200 ° C., the heat treatment time is 5 minutes, and the heating rate is 30 ° C./min. In the first mixed powder, 100 parts by weight of the primary zinc borohydride powder after heat treatment, 3 parts of Ti metal powder, 2 parts of Al metal powder, 1 part of Ni metal powder, and 8 parts of Cu metal powder are calculated in terms of parts by weight. Serving. The second ball milling of the first mixed powder is specifically: the ball-to-material ratio is 8: 1, the ball milling atmosphere is an argon atmosphere, the ball milling speed is 700 r / min, the ball milling time is 80 minutes, during the ball milling process, each ball milling is 10 minutes, and the ball milling is suspended for 2 minutes. During the ball milling process, the temperature in the ball mill tank is controlled below 200 ° C. The second heat treatment of the second mixed powder is specifically: the heat treatment atmosphere is a hydrogen atmosphere, the heat treatment temperature is 180 ° C., the heat treatment time is 4 minutes, and the heating rate is 30 ° C./min. The third ball milling of the third mixed powder is specifically: the ball-to-material ratio is 10: 1, the ball milling atmosphere is argon, the ball milling speed is 850r / min, the ball milling time is 100min, during the ball milling process, each ball milling is 5min, and the ball milling is suspended for 2min. During the ball milling process, the temperature in the ball mill tank is controlled below 200 ° C. The third heat treatment of the fourth mixed powder is specifically: the heat treatment atmosphere is a hydrogen atmosphere, the heat treatment temperature is 160 ° C., the heat treatment time is 4 minutes, and the heating rate is 30 ° C./min.

Example 2

The zinc borohydride-based hydrogen storage material is prepared by providing: NaBH ₄ and ZnCl ₂ raw material powders; first ball milling the NaBH ₄ and ZnCl ₂ raw material powders to obtain primary zinc borohydride powder; First heat treatment; providing Ti, Al, Ni, and Cu metal powders; mixing Ti, Al, Ni, and Cu metal powders and primary zinc borohydride powders after heat treatment to obtain a first mixed powder; Ball milling to obtain a second mixed powder; second heat treatment of the second mixed powder to obtain a third mixed powder; third ball milling of the third mixed powder to obtain a fourth mixed powder; and third heat treatment to the fourth mixed powder. The first ball milling of NaBH ₄ and ZnCl ₂ raw powder is specifically: the ball-to-material ratio is 7: 1, the ball milling atmosphere is argon, the ball milling speed is 600 r / min, the ball milling time is 180 min, and each ball milling during the ball milling process is 15 min. Pause the ball mill for 4 minutes, and control the temperature in the ball mill tank below 200 ° C during the ball mill. The first heat treatment of the primary zinc borohydride powder is specifically: the heat treatment atmosphere is a hydrogen atmosphere, the heat treatment temperature is 250 ° C., the heat treatment time is 10 minutes, and the heating rate is 40 ° C./min. In the first mixed powder, 120 parts by weight of primary zinc borohydride powder, 5 parts of Ti metal powder, 4 parts of Al metal powder, 3 parts of Ni metal powder, and 10 parts of Cu metal powder are calculated by weight part. Serving. The second ball milling of the first mixed powder is specifically: the ball-to-material ratio is 10: 1, the ball milling atmosphere is argon, the ball milling speed is 800r / min, the ball milling time is 100min, during the ball milling process, each ball milling is 15min, and the ball milling is suspended for 4min. During the ball milling process, the temperature in the ball mill tank is controlled below 200 ° C. The second heat treatment of the second mixed powder is specifically: the heat treatment atmosphere is a hydrogen atmosphere, the heat treatment temperature is 220 ° C., the heat treatment time is 8 minutes, and the heating rate is 40 ° C./min. The third ball milling of the third mixed powder is specifically: the ball-to-material ratio is 12: 1, the ball milling atmosphere is argon, the ball milling speed is 1000 r / min, the ball milling time is 150 minutes, during the ball milling process, each ball milling is 10 minutes, and the ball milling is suspended for 4 minutes. During the ball milling process, the temperature in the ball mill tank is controlled below 200 ° C. The third heat treatment of the fourth mixed powder is specifically: the heat treatment atmosphere is a hydrogen atmosphere, the heat treatment temperature is 200 ° C., the heat treatment time is 8 minutes, and the heating rate is 40 ° C./min.

Example 3

The zinc borohydride-based hydrogen storage material is prepared by providing: NaBH ₄ and ZnCl ₂ raw material powders; first ball milling the NaBH ₄ and ZnCl ₂ raw material powders to obtain primary zinc borohydride powder; First heat treatment; providing Ti, Al, Ni, and Cu metal powders; mixing Ti, Al, Ni, and Cu metal powders and primary zinc borohydride powders after heat treatment to obtain a first mixed powder; Ball milling to obtain a second mixed powder; second heat treatment of the second mixed powder to obtain a third mixed powder; third ball milling of the third mixed powder to obtain a fourth mixed powder; and third heat treatment to the fourth mixed powder. The first ball milling of NaBH ₄ and ZnCl ₂ raw powder is specifically: the ball-to-material ratio is 6: 1, the ball milling atmosphere is argon, the ball milling speed is 550r / min, the ball milling time is 160min, and each ball milling during the ball milling process is 12min, Pause the ball mill for 3 minutes, and control the temperature in the ball mill tank below 200 ° C during the ball mill. The first heat treatment of the primary zinc borohydride powder is specifically: the heat treatment atmosphere is a hydrogen atmosphere, the heat treatment temperature is 220 ° C., the heat treatment time is 8 minutes, and the heating rate is 35 ° C./min. In the first mixed powder, 110 parts by weight of the primary zinc borohydride powder after heat treatment, 4 parts by Ti metal powder, 3 parts by Al metal powder, 2 parts by Ni metal powder, and 9 parts by Cu metal powder are calculated in terms of parts by weight. Serving. The second ball milling of the first mixed powder is specifically: the ball-to-material ratio is 9: 1, the ball milling atmosphere is argon, the ball milling speed is 750 r / min, the ball milling time is 90 minutes, during the ball milling process, each ball milling is 12 minutes, and the ball milling is suspended for 3 minutes During the ball milling process, the temperature in the ball mill tank is controlled below 200 ° C. The second heat treatment of the second mixed powder is specifically: the heat treatment atmosphere is a hydrogen atmosphere, the heat treatment temperature is 200 ° C., the heat treatment time is 6 minutes, and the heating rate is 35 ° C./min. The third ball milling of the third mixed powder is as follows: the ball-to-material ratio is 11: 1, the ball milling atmosphere is argon, the ball milling speed is 900 r / min, the ball milling time is 120 minutes, during the ball milling process, each ball milling is 8 minutes, and the ball milling is suspended for 3 minutes. During the ball milling process, the temperature in the ball mill tank is controlled below 200 ° C. The third heat treatment of the fourth mixed powder is specifically: the heat treatment atmosphere is a hydrogen atmosphere, the heat treatment temperature is 180 ° C., the heat treatment time is 6 min, and the heating rate is 3 ° C./min.

Example 4

The zinc borohydride-based hydrogen storage material is prepared by providing: NaBH ₄ and ZnCl ₂ raw material powders; first ball milling the NaBH ₄ and ZnCl ₂ raw material powders to obtain primary zinc borohydride powder; First heat treatment; providing Ti, Al, Ni, and Cu metal powders; mixing Ti, Al, Ni, and Cu metal powders and primary zinc borohydride powders after heat treatment to obtain a first mixed powder; Ball milling to obtain a second mixed powder; second heat treatment of the second mixed powder to obtain a third mixed powder; third ball milling of the third mixed powder to obtain a fourth mixed powder; and third heat treatment to the fourth mixed powder. The first ball milling of NaBH ₄ and ZnCl ₂ raw material powder is specifically: the ball-to-material ratio is 8: 1, the ball milling atmosphere is argon, the ball milling speed is 800r / min, the ball milling time is 210min, and each ball milling during the ball milling process is 20min. Pause the ball mill for 5 minutes without controlling the temperature in the ball mill tank. The first heat treatment of the primary zinc borohydride powder is specifically: the heat treatment atmosphere is a hydrogen atmosphere, the heat treatment temperature is 220 ° C., the heat treatment time is 8 minutes, and the heating rate is 35 ° C./min. In the first mixed powder, 110 parts by weight of the primary zinc borohydride powder after heat treatment, 4 parts by Ti metal powder, 3 parts by Al metal powder, 2 parts by Ni metal powder, and 9 parts by Cu metal powder are calculated in terms of parts by weight. Serving. The second ball milling of the first mixed powder is specifically: the ball-to-material ratio is 9: 1, the ball milling atmosphere is argon, the ball milling speed is 750 r / min, the ball milling time is 90 minutes, during the ball milling process, each ball milling is 12 minutes, and the ball milling is suspended for 3 minutes. During the ball milling process, the temperature in the ball mill tank is controlled below 200 ° C. The second heat treatment of the second mixed powder is specifically: the heat treatment atmosphere is a hydrogen atmosphere, the heat treatment temperature is 200 ° C., the heat treatment time is 6 minutes, and the heating rate is 35 ° C./min. The third ball milling of the third mixed powder is specifically: the ball-to-material ratio is 11: 1, the ball milling atmosphere is an argon atmosphere, the ball milling speed is 900 r / min, the ball milling time is 120 minutes, during the ball milling process, each ball milling is 8 minutes, and the ball milling is suspended for 3 minutes. During the ball milling process, the temperature in the ball mill tank is controlled below 200 ° C. The third heat treatment of the fourth mixed powder is specifically: the heat treatment atmosphere is a hydrogen atmosphere, the heat treatment temperature is 180 ° C., the heat treatment time is 6 min, and the heating rate is 3 ° C./min.

Example 5

The zinc borohydride-based hydrogen storage material is prepared by providing: NaBH ₄ and ZnCl ₂ raw material powders; first ball milling the NaBH ₄ and ZnCl ₂ raw material powders to obtain primary zinc borohydride powder; First heat treatment; providing Ti, Al, Ni, and Cu metal powders; mixing Ti, Al, Ni, and Cu metal powders and primary zinc borohydride powders after heat treatment to obtain a first mixed powder; Ball milling to obtain a second mixed powder; second heat treatment of the second mixed powder to obtain a third mixed powder; third ball milling of the third mixed powder to obtain a fourth mixed powder; and third heat treatment to the fourth mixed powder. The first ball milling of NaBH ₄ and ZnCl ₂ raw powder is specifically: the ball-to-material ratio is 6: 1, the ball milling atmosphere is argon, the ball milling speed is 550r / min, the ball milling time is 160min, and each ball milling during the ball milling process is 12min, Pause the ball mill for 3 minutes, and control the temperature in the ball mill tank below 200 ° C during the ball mill. The first heat treatment of the primary zinc borohydride powder is specifically: the heat treatment atmosphere is a hydrogen atmosphere, the heat treatment temperature is 300 ° C., the heat treatment time is 20 minutes, and the heating rate is 50 ° C./min. In the first mixed powder, 150 parts by weight of the primary zinc borohydride powder, 2 parts of Ti metal powder, 1 part of Al metal powder, 0 parts of Ni metal powder, and 5 parts of Cu metal powder were calculated based on parts by weight. Serving. The second ball milling of the first mixed powder is specifically: the ball-to-material ratio is 9: 1, the ball milling atmosphere is argon, the ball milling speed is 750 r / min, the ball milling time is 90 minutes, during the ball milling process, each ball milling is 12 minutes, and the ball milling is suspended for 3 minutes. During the ball milling process, the temperature in the ball mill tank is controlled below 200 ° C. The second heat treatment of the second mixed powder is specifically: the heat treatment atmosphere is a hydrogen atmosphere, the heat treatment temperature is 200 ° C., the heat treatment time is 6 minutes, and the heating rate is 35 ° C./min. The third ball milling of the third mixed powder is specifically: the ball-to-material ratio is 11: 1, the ball milling atmosphere is an argon atmosphere, the ball milling speed is 900 r / min, the ball milling time is 120 minutes, during the ball milling process, each ball milling is 8 minutes, and the ball milling is suspended for 3 minutes. During the ball milling process, the temperature in the ball mill tank is controlled below 200 ° C. The third heat treatment of the fourth mixed powder is specifically: the heat treatment atmosphere is a hydrogen atmosphere, the heat treatment temperature is 180 ° C., the heat treatment time is 6 min, and the heating rate is 3 ° C./min.

Example 6

The zinc borohydride-based hydrogen storage material is prepared by providing: NaBH ₄ and ZnCl ₂ raw material powders; first ball milling the NaBH ₄ and ZnCl ₂ raw material powders to obtain primary zinc borohydride powder; First heat treatment; providing Ti, Al, Ni, and Cu metal powders; mixing Ti, Al, Ni, and Cu metal powders and primary zinc borohydride powders after heat treatment to obtain a first mixed powder; Ball milling to obtain a second mixed powder; second heat treatment of the second mixed powder to obtain a third mixed powder; third ball milling of the third mixed powder to obtain a fourth mixed powder; and third heat treatment to the fourth mixed powder. The first ball milling of NaBH ₄ and ZnCl ₂ raw powder is specifically: the ball-to-material ratio is 6: 1, the ball milling atmosphere is argon, the ball milling speed is 550r / min, the ball milling time is 160min, and each ball milling during the ball milling process is 12min, Pause the ball mill for 3 minutes, and control the temperature in the ball mill tank below 200 ° C during the ball mill. The first heat treatment of the primary zinc borohydride powder is specifically: the heat treatment atmosphere is a hydrogen atmosphere, the heat treatment temperature is 220 ° C., the heat treatment time is 8 minutes, and the heating rate is 35 ° C./min. In the first mixed powder, 110 parts by weight of the primary zinc borohydride powder after heat treatment, 4 parts by Ti metal powder, 3 parts by Al metal powder, 2 parts by Ni metal powder, and 9 parts by Cu metal powder are calculated in terms of parts by weight. Serving. The second ball milling of the first mixed powder is specifically: the ball-to-material ratio is 15: 1, the ball milling atmosphere is argon, the ball milling speed is 1000 r / min, the ball milling time is 120 minutes, during the ball milling process, each ball milling is 20 minutes, and the ball milling is suspended for 8 minutes. During the ball milling process, the temperature in the ball mill tank is controlled below 200 ° C. The second heat treatment of the second mixed powder is specifically: the heat treatment atmosphere is a hydrogen atmosphere, the heat treatment temperature is 250 ° C., the heat treatment time is 10 minutes, and the heating rate is 50 ° C./min. The third ball milling of the third mixed powder is specifically: the ball-to-material ratio is 11: 1, the ball milling atmosphere is an argon atmosphere, the ball milling speed is 900 r / min, the ball milling time is 120 minutes, during the ball milling process, each ball milling is 8 minutes, and the ball milling is suspended for 3 minutes. During the ball milling process, the temperature in the ball mill tank is controlled below 200 ° C. The third heat treatment of the fourth mixed powder is specifically: the heat treatment atmosphere is a hydrogen atmosphere, the heat treatment temperature is 180 ° C., the heat treatment time is 6 min, and the heating rate is 3 ° C./min.

Example 7

The zinc borohydride-based hydrogen storage material is prepared by providing: NaBH ₄ and ZnCl ₂ raw material powders; first ball milling the NaBH ₄ and ZnCl ₂ raw material powders to obtain primary zinc borohydride powder; First heat treatment; providing Ti, Al, Ni, and Cu metal powders; mixing Ti, Al, Ni, and Cu metal powders and primary zinc borohydride powders after heat treatment to obtain a first mixed powder; Ball milling to obtain a second mixed powder; second heat treatment of the second mixed powder to obtain a third mixed powder; third ball milling of the third mixed powder to obtain a fourth mixed powder; and third heat treatment to the fourth mixed powder. The first ball milling of NaBH ₄ and ZnCl ₂ raw powder is specifically: the ball-to-material ratio is 6: 1, the ball milling atmosphere is argon, the ball milling speed is 550r / min, the ball milling time is 160min, and each ball milling during the ball milling process is 12min, Pause the ball mill for 3 minutes, and control the temperature in the ball mill tank below 200 ° C during the ball mill. The first heat treatment of the primary zinc borohydride powder is specifically: the heat treatment atmosphere is a hydrogen atmosphere, the heat treatment temperature is 220 ° C., the heat treatment time is 8 minutes, and the heating rate is 35 ° C./min. In the first mixed powder, 110 parts by weight of the primary zinc borohydride powder after heat treatment, 4 parts by Ti metal powder, 3 parts by Al metal powder, 2 parts by Ni metal powder, and 9 parts by Cu metal powder are calculated in terms of parts by weight. Serving. The second ball milling of the first mixed powder is specifically: the ball-to-material ratio is 9: 1, the ball milling atmosphere is argon, the ball milling speed is 750 r / min, the ball milling time is 90 minutes, during the ball milling process, each ball milling is 12 minutes, and the ball milling is suspended for 3 minutes. During the ball milling process, the temperature in the ball mill tank is controlled below 200 ° C. The second heat treatment of the second mixed powder is specifically: the heat treatment atmosphere is a hydrogen atmosphere, the heat treatment temperature is 200 ° C., the heat treatment time is 6 minutes, and the heating rate is 35 ° C./min. The third ball milling of the third mixed powder is specifically: the ball-to-material ratio is 15: 1, the ball milling atmosphere is argon, the ball milling speed is 1500r / min, the ball milling time is 200min, during the ball milling process, each ball milling is 20min, and the ball milling is suspended for 8min. During the ball milling process, the temperature in the ball mill tank is controlled below 200 ° C. The third heat treatment of the fourth mixed powder is specifically: the heat treatment atmosphere is a hydrogen atmosphere, the heat treatment temperature is 150 ° C., the heat treatment time is 10 minutes, and the temperature increase rate is 20 ° C./min.

The hydrogen absorption percentage test and the hydrogen absorption percentage test after 100 cycles (100 hydrogen absorption and desorption) at room temperature were performed on Examples 1-7. The test method is a method known in the art, and the test results are based on Example 1. Normalized, the test results are listed in Table 1.

Table 1

The foregoing description of specific exemplary embodiments of the present invention has been provided for the purposes of illustration and illustration. These descriptions are not intended to limit the invention to the precise forms disclosed, and it is apparent that many changes and modifications can be made in light of the above teachings. The purpose of selecting and describing the exemplary embodiments is to explain the specific principles of the present invention and its practical application, so that those skilled in the art can implement and utilize the various exemplary embodiments of the present invention and various different Choose and change. It is intended that the scope of the invention be defined by the Claims and their equivalents.

Claims

A zinc borohydride hydrogen storage material is characterized in that the zinc borohydride hydrogen storage material is prepared by the following method:

Provide NaBH 4 and ZnCl 2 raw material powder;

Performing a first ball milling on the NaBH 4 and ZnCl 2 raw material powders to obtain a primary zinc borohydride powder;

Performing a first heat treatment on the primary zinc borohydride powder;

Provide Ti, Al, Ni and Cu metal powder;

Mixing the Ti, Al, Ni, and Cu metal powders and the primary zinc borohydride powder after heat treatment to obtain a first mixed powder;

Performing a second ball milling on the first mixed powder to obtain a second mixed powder;

Performing a second heat treatment on the second mixed powder to obtain a third mixed powder;

Performing a third ball milling on the third mixed powder to obtain a fourth mixed powder;

The fourth mixed powder is subjected to a third heat treatment.
The zinc borohydride-based hydrogen storage material according to claim 1, wherein the first ball milling of the NaBH 4 and ZnCl 2 raw material powder is specifically: a ball-to-material ratio of 5: 1-7: 1, and a ball milling atmosphere. It is an argon atmosphere, the ball milling speed is 500-600r / min, the ball milling time is 150-180min, during the ball milling process, each ball milling is 10-15min, the ball milling is suspended for 2-4min, and the temperature in the ball milling tank is controlled below 200 ℃ .
The zinc borohydride-based hydrogen storage material according to claim 1, wherein the first heat treatment of the primary zinc borohydride powder is specifically: the heat treatment atmosphere is a hydrogen atmosphere, the heat treatment temperature is 200-250 ° C, and the heat treatment time It is 5-10min, and the heating rate is 30-40 ° C / min.
The zinc borohydride-based hydrogen storage material according to claim 1, wherein in the first mixed powder, the primary zinc borohydride powder after heat treatment accounts for 100-120 parts by weight, and Ti Metal powder accounts for 3-5 parts, Al metal powder accounts for 2-4 parts, Ni metal powder accounts for 1-3 parts, and Cu metal powder accounts for 8-10 parts.
The zinc borohydride-based hydrogen storage material according to claim 1, wherein the second ball milling of the first mixed powder is specifically: the ball-to-material ratio is 8: 1-10: 1, and the ball milling atmosphere is argon. Atmosphere, ball milling speed is 700-800r / min, ball milling time is 80-100min, during the ball milling process, each ball milling is 10-15min, the ball milling is suspended for 2-4min, and the temperature in the ball milling tank is controlled below 200 ° C during the ball milling process.
The zinc borohydride-based hydrogen storage material according to claim 1, wherein the second heat treatment of the second mixed powder is specifically: the heat treatment atmosphere is a hydrogen atmosphere, the heat treatment temperature is 180-220 ° C, and the heat treatment time is 4-8min, heating rate is 30-40 ℃ / min.
The zinc borohydride-based hydrogen storage material according to claim 1, wherein the third ball milling of the third mixed powder is specifically: the ball-to-material ratio is 10: 1-12: 1, and the ball milling atmosphere is argon. Atmosphere, ball milling speed is 850-1000r / min, ball milling time is 100-150min, during the ball milling process, each ball milling is 5-10min, the ball milling is suspended for 2-4min, and the temperature in the ball milling tank is controlled below 200 ° C during the ball milling process.
The zinc borohydride-based hydrogen storage material according to claim 1, wherein the third heat treatment of the fourth mixed powder is specifically: the heat treatment atmosphere is a hydrogen atmosphere, the heat treatment temperature is 160-200 ° C, and the heat treatment time is 4-8min, heating rate is 30-40 ℃ / min.