CN103496669B - B-N-H system hydrogen storage material and preparation method thereof - Google Patents

B-N-H system hydrogen storage material and preparation method thereof Download PDF

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CN103496669B
CN103496669B CN201310400675.0A CN201310400675A CN103496669B CN 103496669 B CN103496669 B CN 103496669B CN 201310400675 A CN201310400675 A CN 201310400675A CN 103496669 B CN103496669 B CN 103496669B
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hydrogen storage
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CN103496669A (en
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欧阳柳章
黄建媚
朱敏
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South China University of Technology SCUT
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Abstract

The invention discloses a B-N-H system hydrogen storage material with a chemical formula of Zr(BH4)4.8NH3. The invention further discloses a preparation method for the hydrogen storage material. The preparation method comprises the following steps: (1) preparing Zr(BH4)4; and (2) preparing Zr(BH4)4.8NH3 by subjecting zirconium hydroborate and ammonia to a contact reaction at a temperature lower than 10 DEG C for 0.5 to 12 h in an inert atmosphere or under vacuum. According to the invention, raw materials used in the preparation method are easy to prepare, synthetic process is simple and is easy to realize, and prepared Zr(BH4)4.8NH3 can be decomposed at a low temperature so as to obtain considerable hydrogen and can be used as an ideal hydrogen supplying medium.

Description

A kind of B-N-H system hydrogen storage material and preparation method thereof
Technical field
The present invention relates to hydrogen storage material and preparation method thereof, particularly a kind of B-N-H system hydrogen storage material and preparation method thereof.
Background technology
The activity in production that the energy is the mankind and social activity provide power, have promoted the development and progress of human history.Due to the sharp increase of industrial development and population, depending on unduly and overexploitation of a large amount of fossil energy, makes facing mankind huge fossil energy shortage.In addition, a large amount of fossil energy that uses causes serious environmental pollution, constitutes great threat to human lives.In the face of the dual-pressure of increasingly serious energy dilemma and environmental pollution, develop new continuable green energy resource extremely urgent.As a kind of desirable new forms of energy carrier, the advantages such as hydrogen has cleanliness without any pollution, and fuel value is high, renewable, thus the research of hydrogen energy source system attracts tremendous attention.In the development and utilization of Hydrogen Energy, the link of most critical is the storage of hydrogen.Wherein, solid-state storage hydrogen, because its energy density is high and security good, is considered to a kind of hydrogen storage mode that most is promising.
The hydroborates of alkali and alkaline earth metal ions has high theoretical hydrogen-storage amount (as LiBH because of it 4for 18.4wt%, Mg (BH 4) 2for 14.9wt%) and become the study hotspot of hydrogen storage material, but problem constrains its large-scale application as hydrogen storage material such as the hydrogen discharging temperature caused due to thermodynamic property and the kinetic property of material itself is high, hydrogen discharging rate is slow.Therefore, investigator wants to find all more suitable material of a kind of thermodynamic and kinetic properties advances hydrogen energy source fast development and utilization as new hydrogen storage material.Research finds, transition metal hydroborate has lower Enthalpies of Formation compared to alkali and alkaline earth metal ions hydroborate, and this is thermodynamically favourable.Therefore, in succession there is the research to transition metal hydroborate, as Y (BH 4) 4, Sc (BH 4) 4.But most transition metal hydroborate is in room temperature instability or directly volatilize, as Ti (BH 4) 3, V (BH 4) 3, Fe (BH 4) 3, this just hinders transition metal hydroborate and applies as the research of solid hydrogen storage material.
In order to address this problem, researchist finds, by carrying out ammonification to hydroborate, mass transfer that is unstable under room temperature condition or distillation can be become stable solid, as by Al (BH 4) 3gas ammonification changes Al (BH into 4) 36NH 3solid.Because the hydrogen content of ammonia reaches 9.1wt%, by itself and hydroborate complexing, the hydrogen storage capability of material can also be improved.Meanwhile, owing to there is electropositive N-H and electronegative B-H, H in same a part δ+and H δ-in conjunction with releasing hydrogen gas, the release temperature of hydrogen in metal borohydride is caused greatly to reduce, as recent development M (BH 4) xnNH 3(M=Li, Mg, Ca).Investigator is separately had to find, first transition metal chloride can be carried out ammonification, carry out ball-milling again with hydroborate and obtain stable transition metal hydroborate amide, but the drawback of the method is the muriate generated to be difficult to be separated removing, have impact on the capacity of system.
Summary of the invention
In order to overcome the above-mentioned shortcoming of prior art with not enough, the object of the present invention is to provide a kind of preparation method of B-N-H system hydrogen storage material, raw material is easy to preparation, and synthesis technique is simple, is easy to realize.
Another object of the present invention is to provide a kind of B-N-H system hydrogen storage material, decompose at a lower temperature and obtain a large amount of hydrogen, efficient stable.
Object of the present invention is achieved through the following technical solutions:
A preparation method for B-N-H system hydrogen storage material, comprises the following steps:
(1) Zr (BH is prepared 4) 4;
(2) Zr (BH is prepared 4) 48NH 3: under inert atmosphere or vacuum condition, by Zr (BH 4) 4with ammonia lower than 10 degrees Celsius of lower contact reactss, the reaction times is 0.5 ~ 12 hour, obtains Zr (BH 4) 48NH 3.
Step (1) described preparation Zr (BH 4) 4, be specially:
Under inert atmosphere or vacuum condition, by zirconium halide and hydroborate lower than 20 degrees Celsius of ball millings, obtain Zr (BH 4) 4; The mol ratio of described zirconium halide and hydroborate is 1:0.5 ~ 1:10.
Described ball milling, is specially: ratio of grinding media to material is 5:1 ~ 50:1, and the speed of ball milling is 50 ~ 500 revs/min, and Ball-milling Time is 0.5 ~ 12 hour, and operational mode is for alternately to restart, and alt time is 6 ~ 30 minutes, and the dead time is 6 ~ 30 minutes.
Described hydroborate is any one in lithium borohydride, sodium borohydride, POTASSIUM BOROHYDRIDE, magnesium borohydride, calcium borohydride or double ion hydroborate.
Described in step (2) by hydroboration zirconium and ammonia lower than 10 degrees Celsius of lower contact reactss, be specially:
By Zr (BH 4) 4in the reactor of crystal tape loaded cock, be 5 ~ 80ml min with flow velocity in an inert atmosphere or after vacuumizing -1pass into dry ammonia, lower than 10 degrees Celsius of lower contact reactss.
A kind of B-N-H system hydrogen storage material, its chemical formula is Zr (BH 4) 48NH 3.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) preparation method of B-N-H system hydrogen storage material of the present invention, by low temperature ball grinding technique, low melting point prepared by ball milling, volatile Zr (BH 4) 4crystal fast and ammonia complexing prepare Zr (BH 4) 48NH 3, raw material is easy to preparation, and synthesis technique is simple, is easy to realize.
(2) Zr (BH for preparing of the present invention 4) 48NH 3hydrogen storage material, efficient stable, is heated to 60 DEG C and can obtains hydrogen, is greater than the hydrogen of 9wt% 60 ~ 300 DEG C of releases.
Accompanying drawing explanation
Fig. 1 is the high resolution x-ray diffractogram of powder of B-N-H system hydrogen storage material prepared by embodiments of the invention.
Fig. 2 is the mass spectrum-thermolysis weightlessness figure of B-N-H system hydrogen storage material prepared by embodiments of the invention.
Fig. 3 is the alternating temperature air release graphic representation of B-N-H system hydrogen storage material prepared by embodiments of the invention.
Fig. 4 is the constant temperature air release graphic representation of B-N-H system hydrogen storage material prepared by embodiments of the invention.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
The preparation method of the B-N-H system hydrogen storage material of the present embodiment, comprises the following steps:
(1) Zr (BH is prepared 4) 4: in glove box, get anhydrous ZrCl 4with LiBH 4mixing, the mol ratio of described zirconium chloride and lithium borohydride is 1:6; After loading ball grinder, ball milling is taken out in sealing.Ball milling carries out in inert atmosphere or vacuum, and ratio of grinding media to material is 30:1, and the speed of ball milling is 300 revs/min, and Ball-milling Time is 6 hours, and ball milling temperature is 15 degrees Celsius.Join Stainless Steel ball milling steel ball, diameter is at 0.5 ~ 2 centimetre.Operational mode is for alternately to restart, and alt time is 6 minutes, and the dead time is 6 minutes.Complete can the collection on lid of ball milling obtains water white transparency Zr (BH 4) 4crystal.
(2) Zr (BH is prepared 4) 48NH 3: by Zr (BH in glove box 4) 4in the reactor of crystal tape loaded cock, taking out the reactor closed, is 20ml min with flow velocity after vacuumizing -1pass into dry ammonia, 3 degrees Celsius of lower sustained reactions 8 hours, Zr (BH can be obtained 4) 48NH 3white powder.
Fig. 1 is Zr (BH prepared by the present embodiment 4) 48NH 3high resolution x-ray diffractogram of powder, show that crystallinity is very good, its gas mass spectrum-thermolysis Weight loss data is shown in Fig. 2.Mass spectrum display Zr (BH 4) 48NH 3decompose from 60 degrees Celsius, 300 degrees centigrade react completely, and are mainly release hydrogen, have a small amount of ammonia to discharge, do not have borine to discharge.Thermogravimetric shows total weightlessness and is about 22.8wt%.Zr (BH prepared by the present embodiment 4) 48NH 3alternating temperature air release curve see Fig. 3,0.051 moles per gram gas can be discharged with 5 degrees celsius/minute temperature programmings to 300 degree Celsius; Constant temperature air release curve is shown in Fig. 4, and 90 degrees Celsius, 110 degrees Celsius, 130 degrees Celsius and 150 degrees Celsius of constant temperature are tested and within 6 hours, released 0.021 moles per gram, 0.032 moles per gram, 0.042 moles per gram, 0.048 moles per gram gas respectively.
Embodiment 2
The preparation method of the B-N-H system hydrogen storage material of the present embodiment, comprises the following steps:
(1) Zr (BH is prepared 4) 4: in glove box, get anhydrous ZrCl 4with LiBH 4mixing, the mol ratio of described zirconium chloride and lithium borohydride is 1:4; After loading ball grinder, ball milling is taken out in sealing.Ball milling carries out in inert atmosphere or vacuum, and ratio of grinding media to material is 40:1, and the speed of ball milling is 400 revs/min, and Ball-milling Time is 4 hours, and ball milling temperature is 10 degrees Celsius.Join Stainless Steel ball milling steel ball, diameter is at 0.5 ~ 2 centimetre.Operational mode is for alternately to restart, and alt time is 12 minutes, and the dead time is 12 minutes.Complete can the collection on lid of ball milling obtains water white transparency Zr (BH 4) 4crystal.
(2) Zr (BH is prepared 4) 48NH 3: by Zr (BH in glove box 4) 4in the reactor of crystal tape loaded cock, taking out the reactor closed, is 40ml min with flow velocity after vacuumizing -1pass into dry ammonia, sustained reaction 6 hours, can obtain Zr (BH at 5 c 4) 48NH 3white powder.
B-N-H system hydrogen storage material test result prepared by the present embodiment is similar to Example 1.
Embodiment 3
The preparation method of the B-N-H system hydrogen storage material of the present embodiment, comprises the following steps:
(1) Zr (BH is prepared 4) 4: in glove box, get anhydrous ZrCl 4with LiBH 4mixing, the mol ratio of described zirconium chloride and lithium borohydride is 1:2; After loading ball grinder, ball milling is taken out in sealing.Ball milling carries out in inert atmosphere or vacuum, and ratio of grinding media to material is 20:1, and the speed of ball milling is 500 revs/min, and Ball-milling Time is 2 hours, and ball milling temperature is 10 degrees Celsius.Join Stainless Steel ball milling steel ball, diameter is at 0.5 ~ 2 centimetre.Operational mode is for alternately to restart, and alt time is 6 minutes, and the dead time is 6 minutes.Complete can the collection on lid of ball milling obtains water white transparency Zr (BH 4) 4crystal.
(2) Zr (BH is prepared 4) 48NH 3: by Zr (BH in glove box 4) 4in the reactor of crystal tape loaded cock, taking out the reactor closed, is 20ml min with flow velocity after vacuumizing -1pass into dry ammonia, 10 degrees Celsius of lower sustained reactions 4 hours, Zr (BH can be obtained 4) 48NH 3white powder.
B-N-H system hydrogen storage material test result prepared by the present embodiment is similar to Example 1.
Embodiment 4
The preparation method of the B-N-H system hydrogen storage material of the present embodiment, comprises the following steps:
(1) Zr (BH is prepared 4) 4: in glove box, get anhydrous ZrCl 4with LiBH 4mixing, the mol ratio of described zirconium chloride and lithium borohydride is 1:8; After loading ball grinder, ball milling is taken out in sealing.Ball milling carries out in inert atmosphere or vacuum, and ratio of grinding media to material is 10:1, and the speed of ball milling is 300 revs/min, and Ball-milling Time is 8 hours, and ball milling temperature is 10 degrees Celsius.Join Stainless Steel ball milling steel ball, diameter is at 0.5 ~ 2 centimetre.Operational mode is for alternately to restart, and alt time is 12 minutes, and the dead time is 12 minutes.Complete can the collection on lid of ball milling obtains water white transparency Zr (BH 4) 4crystal.
(2) Zr (BH is prepared 4) 48NH 3: by Zr (BH in glove box 4) 4in the reactor of crystal tape loaded cock, taking out the reactor closed, is 60ml min with flow velocity after vacuumizing -1pass into dry ammonia, sustained reaction 4 hours, can obtain Zr (BH at 5 c 4) 48NH 3white powder.
B-N-H system hydrogen storage material test result prepared by the present embodiment is similar to Example 1.
Embodiment 5
The preparation method of the B-N-H system hydrogen storage material of the present embodiment, comprises the following steps:
(1) Zr (BH is prepared 4) 4: in glove box, get anhydrous ZrCl 4with LiBH 4mixing, the mol ratio of described zirconium chloride and lithium borohydride is 1:1; After loading ball grinder, ball milling is taken out in sealing.Ball milling carries out in inert atmosphere or vacuum, and ratio of grinding media to material is 50:1, and the speed of ball milling is 100 revs/min, and Ball-milling Time is 12 hours, and ball milling temperature is 5 degrees Celsius.Join Stainless Steel ball milling steel ball, diameter is at 0.5 ~ 2 centimetre.Operational mode is for alternately to restart, and alt time is 30 minutes, and the dead time is 30 minutes.Complete can the collection on lid of ball milling obtains water white transparency Zr (BH 4) 4crystal.
(2) Zr (BH is prepared 4) 48NH 3: by Zr (BH in glove box 4) 4in the reactor of crystal tape loaded cock, taking out the reactor closed, is 80ml min with flow velocity after vacuumizing -1pass into dry ammonia, 3 degrees Celsius of lower sustained reactions 0.5 hour, Zr (BH can be obtained 4) 48NH 3white powder.
B-N-H system hydrogen storage material test result prepared by the present embodiment is similar to Example 1.
Embodiment 6
The preparation method of the B-N-H system hydrogen storage material of the present embodiment, comprises the following steps:
(1) Zr (BH is prepared 4) 4: in glove box, get anhydrous ZrCl 4with LiBH 4mixing, the mol ratio of described zirconium chloride and lithium borohydride is 1:0.5; After loading ball grinder, ball milling is taken out in sealing.Ball milling carries out in inert atmosphere or vacuum, and ratio of grinding media to material is 50:1, and the speed of ball milling is 300 revs/min, and Ball-milling Time is 10 hours, and ball milling temperature is 5 degrees Celsius.Join Stainless Steel ball milling steel ball, diameter is at 0.5 ~ 2 centimetre.Operational mode is for alternately to restart, and alt time is 6 minutes, and the dead time is 6 minutes.Complete can the collection on lid of ball milling obtains water white transparency Zr (BH 4) 4crystal.
(2) Zr (BH is prepared 4) 48NH 3: by Zr (BH in glove box 4) 4in the reactor of crystal tape loaded cock, taking out the reactor closed, is 40ml min with flow velocity after vacuumizing -1pass into dry ammonia, sustained reaction 8 hours, can obtain Zr (BH at 5 c 4) 48NH 3white powder.
B-N-H system hydrogen storage material test result prepared by the present embodiment is similar to Example 1.
Embodiment 7
The preparation method of the B-N-H system hydrogen storage material of the present embodiment, comprises the following steps:
(1) Zr (BH is prepared 4) 4: in glove box, get anhydrous ZrCl 4with LiBH 4mixing, the mol ratio of described zirconium chloride and lithium borohydride is 1:2; After loading ball grinder, ball milling is taken out in sealing.Ball milling carries out in inert atmosphere or vacuum, and ratio of grinding media to material is 5:1, and the speed of ball milling is 300 revs/min, and Ball-milling Time is 12 hours, and ball milling temperature is 15 degrees Celsius.Join Stainless Steel ball milling steel ball, diameter is at 0.5 ~ 2 centimetre.Operational mode is for alternately to restart, and alt time is 30 minutes, and the dead time is 30 minutes.Complete can the collection on lid of ball milling obtains water white transparency Zr (BH 4) 4crystal.
(2) Zr (BH is prepared 4) 48NH 3: by Zr (BH in glove box 4) 4in the reactor of crystal tape loaded cock, taking out the reactor closed, is 5ml min with flow velocity after vacuumizing -1pass into dry ammonia, sustained reaction 12 hours, can obtain Zr (BH at 5 c 4) 48NH 3white powder.
B-N-H system hydrogen storage material test result prepared by the present embodiment is similar to Example 1.
Embodiment 8
The preparation method of the B-N-H system hydrogen storage material of the present embodiment, comprises the following steps:
(1) Zr (BH is prepared 4) 4: in glove box, get anhydrous ZrCl 4with LiBH 4mixing, the mol ratio of described zirconium chloride and lithium borohydride is 1:10; After loading ball grinder, ball milling is taken out in sealing.Ball milling carries out in inert atmosphere or vacuum, and ratio of grinding media to material is between 50:1, and the speed of ball milling is 500 revs/min, and Ball-milling Time is 0.5 hour, and ball milling temperature is 5 degrees Celsius.Join Stainless Steel ball milling steel ball, diameter is at 0.5 ~ 2 centimetre.Operational mode is for alternately to restart, and alt time is 6 minutes, and the dead time is 6 minutes.Complete can the collection on lid of ball milling obtains water white transparency Zr (BH 4) 4crystal.
(2) Zr (BH is prepared 4) 48NH 3: by Zr (BH in glove box 4) 4in the reactor of crystal tape loaded cock, taking out the reactor closed, is 80ml min with flow velocity after passing into rare gas element -1pass into dry ammonia, sustained reaction 2 hours, can obtain Zr (BH at 5 c 4) 48NH 3white powder.
B-N-H system hydrogen storage material test result prepared by the present embodiment is similar to Example 1.
Embodiment 9
The preparation method of the B-N-H system hydrogen storage material of the present embodiment, comprises the following steps:
(1) Zr (BH is prepared 4) 4: in glove box, get anhydrous ZrCl 4with LiBH 4mixing, the mol ratio of described zirconium chloride and lithium borohydride is 1:6; After loading ball grinder, ball milling is taken out in sealing.Ball milling carries out in inert atmosphere or vacuum, and ratio of grinding media to material is between 50:1, and the speed of ball milling is 50 revs/min, and Ball-milling Time is 12 hours, and ball milling temperature is 10 degrees Celsius.Join Stainless Steel ball milling steel ball, diameter is at 0.5 ~ 2 centimetre.Operational mode is for alternately to restart, and alt time is 30 minutes, and the dead time is 30 minutes.Complete can the collection on lid of ball milling obtains water white transparency Zr (BH 4) 4crystal.
(2) Zr (BH is prepared 4) 48NH 3: by Zr (BH in glove box 4) 4in the reactor of crystal tape loaded cock, taking out the reactor closed, is 80ml min with flow velocity after passing into rare gas element -1pass into dry ammonia, sustained reaction 8 hours, can obtain Zr (BH at 5 c 4) 48NH 3white powder.
B-N-H system hydrogen storage material test result prepared by the present embodiment is similar to Example 1.
Above-described embodiment is the present invention's preferably embodiment, but embodiments of the present invention are not limited by the examples, as ZrCl 4other zirconium halides can also be replaced with; Described hydroborate can also in sodium borohydride, POTASSIUM BOROHYDRIDE, magnesium borohydride, calcium borohydride or double ion hydroborate any one; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.

Claims (5)

1. a preparation method for B-N-H system hydrogen storage material, is characterized in that, comprises the following steps:
(1) Zr (BH is prepared 4) 4;
(2) Zr (BH is prepared 4) 48NH 3: by Zr (BH 4) 4in the reactor of crystal tape loaded cock, be 5 ~ 80ml min with flow velocity at inert atmosphere or after vacuumizing -1pass into dry ammonia, lower than 10 degrees Celsius of lower contact reactss, the reaction times is 0.5 ~ 12 hour, obtains Zr (BH 4) 48NH 3.
2. the preparation method of B-N-H system hydrogen storage material according to claim 1, is characterized in that, step (1) described preparation Zr (BH 4) 4, be specially:
Under inert atmosphere or vacuum condition, by zirconium halide and hydroborate lower than 20 degrees Celsius of ball millings, obtain Zr (BH 4) 4; The mol ratio of described zirconium halide and hydroborate is 1:0.5 ~ 1:10.
3. the preparation method of B-N-H system hydrogen storage material according to claim 2, is characterized in that, described ball milling, is specially:
Ratio of grinding media to material is 5:1 ~ 50:1, and the speed of ball milling is 50 ~ 500 revs/min, and Ball-milling Time is 0.5 ~ 12 hour, and operational mode is for alternately to restart, and alt time is 6 ~ 30 minutes, and the dead time is 6 ~ 30 minutes.
4. the preparation method of B-N-H system hydrogen storage material according to claim 2, is characterized in that, described hydroborate is any one in lithium borohydride, sodium borohydride, POTASSIUM BOROHYDRIDE, magnesium borohydride, calcium borohydride or double ion hydroborate.
5. the B-N-H system hydrogen storage material for preparing of the preparation method of claim 1, it is characterized in that, its chemical formula is Zr (BH 4) 48NH 3.
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CN104386745B (en) * 2014-11-03 2015-12-30 安徽工业大学 A kind of preparation method of nano zirconium oxide powder
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CN108285131B (en) * 2018-03-14 2021-09-21 华南理工大学 Method for preparing lithium borohydride by room-temperature solid-phase ball milling
CN108545699B (en) * 2018-04-03 2021-10-22 华南理工大学 Method for directly synthesizing sodium borohydride by room-temperature solid-phase ball milling
CN113670770A (en) * 2021-09-16 2021-11-19 湖北航天化学技术研究所 AlH-containing catalyst3Propellant thermal decomposition detection method

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