CN109666908B - Solid hydrogen storage core and preparation method thereof - Google Patents

Solid hydrogen storage core and preparation method thereof Download PDF

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Publication number
CN109666908B
CN109666908B CN201811448225.8A CN201811448225A CN109666908B CN 109666908 B CN109666908 B CN 109666908B CN 201811448225 A CN201811448225 A CN 201811448225A CN 109666908 B CN109666908 B CN 109666908B
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hydrogen storage
layer
lani
chromium
core
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CN109666908A (en
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韩建
崔龙
米新艳
张克金
于力娜
苏中辉
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FAW Jiefang Automotive Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/508—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by selective and reversible uptake by an appropriate medium, i.e. the uptake being based on physical or chemical sorption phenomena or on reversible chemical reactions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/021—Cleaning or etching treatments
    • C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering

Abstract

The invention discloses a solid hydrogen storage core and a preparation method thereof, belonging to the technical field of fuel cells and mainly aiming at solving the problems that the utilization rate of the existing solid hydrogen storage core to hydrogen storage materials is not high and the storage efficiency of hydrogen is not high; the core body base material is a metal fiber felt, the material is 304 stainless steel, 316L stainless steel or 310S stainless steel, or an iron-chromium-aluminum metal material, the fiber diameter is 1-50 um, the porosity of the fiber felt is 70-90%, and the thickness of the fiber felt is 0.2-2 mm; the core substrate can be in any shape before film coating; the hydrogen storage material is LaNixOr LaNixAl1‑x(ii) a The thickness of the plating layer is 50-2000 nm; the transition layer is metal chromium or titanium, and the thickness is 10-1000 nm.

Description

Solid hydrogen storage core and preparation method thereof
Technical Field
The invention relates to the technical field of fuel cells, in particular to a solid hydrogen storage core and a preparation method thereof.
Background
Among many new energy sources, hydrogen energy is one of the future energy sources with great development potential. Hydrogen energy is a clean renewable energy source and has the characteristics of storage and transportation. At present, it is an ideal vehicle energy source with low pollution and even zero pollution. In the long term, its development may bring about a significant change in the structure of the energy source. However, in practical applications, its storage and transportation is critical. The key point is to find a hydrogen storage method which is efficient, low in cost and capable of being utilized in a large scale.
The existing hydrogen storage methods generally include high-pressure compression hydrogen storage, low-temperature liquid hydrogen storage, metal hydride hydrogen storage, adsorption hydrogen storage, complex hydrogen storage, inorganic hydrogen storage, and organic liquid hydrogen storage. However, the low-temperature liquid hydrogen storage consumes a large amount of cooling energy in the hydrogen liquefaction process, and evaporation loss is inevitably generated in the storage process, so that the storage cost is high. The high-pressure compression hydrogen storage has great potential safety hazard. Compared with high-pressure gaseous hydrogen storage and liquefied hydrogen storage, the solid-state hydrogen storage of the hydrogen storage material can well solve the problems of low hydrogen storage density and poor safety coefficient of the traditional hydrogen storage technology, hydrogen and the material are reacted or adsorbed in the material during hydrogen storage, and the material is heated or decompressed to release the hydrogen when needed. The solid hydrogen storage material has hydrogen storage density about 1000 times that of gaseous hydrogen storage under the same temperature and pressure condition, and has high hydrogen absorbing and releasing speed and high safety. The alloy hydrogen storage material is the most widely used hydrogen storage material at present due to strong hydrogen storage capacity, little pollution, high safety factor and mature preparation process. Alloy hydrogen storage materials store hydrogen in the alloy by the form of metal hydrides. The alloy hydrogen storage material generates an exothermic reaction to absorb hydrogen to generate metal hydride under a certain temperature and hydrogen pressure, and generates an endothermic reaction to release the absorbed hydrogen under the condition of heating. Therefore, the solid hydrogen storage is beneficial to the safe application of hydrogen and has wide application prospect.
Disclosure of Invention
The invention aims to solve the problems that the utilization rate of the existing solid hydrogen storage core body to the hydrogen storage material is not high and the storage efficiency of hydrogen is not high, and in order to achieve the purpose, the invention provides the solid hydrogen storage core body and the preparation method thereof, wherein the solid hydrogen storage core body mainly comprises a core body base material, a transition layer and a hydrogen storage material layer, the transition layer is positioned between the core body base material and the hydrogen storage material layer, and the hydrogen storage material layer is positioned on the surface of the solid hydrogen storage core body;
the core body base material is a metal fiber felt, the material is 304 stainless steel, 316L stainless steel or 310S stainless steel, or an iron-chromium-aluminum metal material, the fiber diameter is 1-50 um, the porosity of the fiber felt is 70-90%, and the thickness of the fiber felt is 0.2-2 mm; the core substrate can be in any shape before film coating; the hydrogen storage material is LaNix(x is 1 to 5) orLaNixAl1-x(x is 0.2 to 0.8); the thickness of the plating layer is 50-2000 nm; the transition layer is metal chromium or titanium, and the thickness is 10-1000 nm.
A method for preparing a solid hydrogen storage core, comprising the steps of:
(1) ion sputtering cleaning process
Ultrasonically cleaning a core body base material, drying the core body base material by using high-purity nitrogen, putting the core body base material into a non-equilibrium magnetron sputtering ion plating furnace chamber, heating to 50-300 ℃, and vacuumizing until the vacuum degree of the furnace chamber is lower than 3 multiplied by 10-3～6×10-3Pa, keeping the temperature for 0.5-5 h, then filling argon to ensure that the vacuum degree of the furnace chamber is 0.2-2 Pa, applying bias voltage to the substrate to be-200-1000V, applying ion source voltage to be 200-1000V, bombarding the surface of the substrate by the ion source to remove the passive film, and cleaning the substrate by ions for 10-120 min;
(2) depositing a transition layer
And starting the current of the chromium target, keeping the working air pressure between 0.2 Pa and 10Pa, keeping the bias voltage of the matrix between-50V and-800V, and depositing chromium on the surface of the core body for 1-20 min, wherein the current of the chromium target is 0.2-10A. The transition layer can also be selected from titanium targets.
(3) Depositing a hydrogen storage layer
The current of the chromium target is adjusted to 0, the matrix bias voltage is between-50V and-800V, and LaNixThe target current is maintained at 0.3-10A, and deposition is carried out for 2-200 min. Depositing LaNi on the surface of the pure chromium layer prepared in the step (2)xAnd a hydrogen storage layer.
The step (3) can also deposit LaNixAl1-xThe hydrogen storage layer is specifically operated by adjusting the current of the chromium target to 0, the bias voltage of the matrix to-50 to-800V and LaNixThe target current is gradually reduced from 10A, the Al target is gradually increased from 0A, and the deposition lasts for 2-200 min; or the Al target is gradually reduced from 5A, and LaNixThe target current is gradually increased from 0A, and the deposition time is 2-200 min. Depositing LaNi on the surface of the pure chromium layer prepared in the step (2)xAl1-xAnd a hydrogen storage layer.
The core body base material of the step (1) is a metal fiber felt, the material is 304, 316L or 310S stainless steel or iron-chromium-aluminum material, the fiber diameter is 1-50 um, the porosity of the fiber felt is 70-90%, and the thickness of the fiber felt is 0.2-2 mm.
The core substrate in the step (1) may be in a flat plate shape, a folded fan shape, a cylindrical shape, a corrugated cylindrical shape, or any other shape before being coated with the film.
The invention has the beneficial effects that:
the invention provides a safe and reliable hydrogen storage core body, which improves the utilization rate of hydrogen storage materials and the storage efficiency of hydrogen.
Drawings
FIG. 1 is a schematic view of a solid state hydrogen storage core material.
Detailed Description
The present invention is described in further detail below with reference to specific examples, which are not to be construed as limiting the scope of the invention as claimed.
Example 1:
method for preparing LaNi by utilizing unbalanced magnetron sputtering ion coating equipmentxAnd (3) hydrogen storage coating, namely ultrasonically cleaning a 316L stainless steel metal fiber felt (the diameter of a fiber is 1um, the thickness of the metal felt is 0.5mm, and the porosity is 85%) sample by weak base, weak acid, deionized water and absolute ethyl alcohol, drying the sample by using high-purity nitrogen, and hanging the sample on a rotary sample rack of a furnace chamber. Heating the furnace chamber to 150 deg.C, and simultaneously vacuumizing to 3 × 10-3Pa, keeping the pressure for 2 hours under the condition, introducing argon gas, keeping the pressure in the furnace chamber at 0.3Pa, biasing to-600V, adding ion source voltage to 800V, and carrying out ion cleaning on the surface of the sample for 30min to remove the passive film on the surface of the stainless steel fiber felt. Adjusting the bias voltage of the substrate to-400V, the current of the chromium target to be 3A and the deposition time to be 5 min; closing the current of the chromium target, and adjusting the bias voltage of the matrix to-600V, LaNixTarget current was adjusted to 5A, deposition time 5min, then substrate bias was adjusted to-400V, LaNixThe target current was adjusted to 3.5A, and the deposition time was 10 min. Tests show that the total thickness of the LaNix plating layer prepared by the embodiment is 0.5 μm, and the bonding force is 80N.
The core body material has rich pore structures, so that hydrogen can be fully contacted with the hydrogen storage material, and the hydrogen can be stored at room temperature of 2.5-3 bar. Can efficiently utilize the hydrogen storage material and improve the storage efficiency of the hydrogen.
Example 2:
method for preparing LaNi by utilizing unbalanced magnetron sputtering ion coating equipmentxAl1-xHydrogen storage coating, wherein a 310S stainless steel metal fiber felt (the diameter of a fiber is 1um, the thickness of the metal felt is 0.3mm, and the porosity is 90%) sample is ultrasonically cleaned by weak base, weak acid, deionized water and absolute ethyl alcohol, then is dried by high-purity nitrogen and is hung on a rotary sample rack of a furnace chamber. Heating the furnace chamber to 200 deg.C, and simultaneously vacuumizing to 3 × 10-3Pa, keeping the pressure for 2 hours under the condition, introducing argon gas, keeping the pressure in the furnace chamber at 0.6Pa, biasing to-600V, adding ion source voltage to 800V, and carrying out ion cleaning on the surface of the sample for 30min to remove the passive film on the surface of the stainless steel fiber felt. Adjusting the bias voltage of the substrate to-400V, the current of the chromium target to be 3A and the deposition time to be 5 min; closing the current of the chromium target, and adjusting the bias voltage of the matrix to-600V, LaNixThe target current was adjusted to 10A and LaNi was gradually decreasedxThe current is reduced to 0A at a rate of 0.5A/min, the Al target current is 0A, the Al target current is gradually increased to 5A at a rate of 0.25A/min, the deposition time is 20min, and tests show that the LaNi prepared by the embodimentxThe total thickness of the plating layer is 0.8 μm, and the binding force is 70N.
The core body material has rich pore structures, so that hydrogen can be fully contacted with the hydrogen storage material, and the hydrogen can be stored at room temperature of 2.5-3 bar. Can efficiently utilize the hydrogen storage material and improve the storage efficiency of the hydrogen.
Example 3:
method for preparing LaNi by utilizing unbalanced magnetron sputtering ion coating equipmentxAnd (3) hydrogen storage coating, namely ultrasonically cleaning a 316L stainless steel metal fiber felt (the diameter of a fiber is 1um, the thickness of the metal felt is 0.5mm, and the porosity is 90%) sample by weak base, weak acid, deionized water and absolute ethyl alcohol, drying the sample by using high-purity nitrogen, and hanging the sample on a rotary sample rack of a furnace chamber. Heating furnace chamber to 250 deg.C, and simultaneously vacuumizing to 3 × 10-3Pa, and keeping for 2h under the condition, and then introducing argon to ensure thatThe pressure in the furnace chamber is 0.3Pa, the bias voltage is increased to-600V, the ion source voltage is increased to 800V, and the surface of the sample is subjected to ion cleaning for 30min to remove the passive film on the surface of the stainless steel fiber felt. Adjusting the bias voltage of the substrate to-500V, the current of the chromium target to be 2A and the deposition time to be 5 min; closing the current of the chromium target, and adjusting the bias voltage of the matrix to-600V, LaNixTarget current was adjusted to 5A, deposition time 5min, then substrate bias was adjusted to-450V, LaNixThe target current was adjusted to 3A and the deposition time was 20 min. The tests show that the LaNi prepared by the examplexThe total thickness of the plating layer is 1 μm, and the binding force is 72N.
The core body material has rich pore structures, so that hydrogen can be fully contacted with the hydrogen storage material, and the hydrogen can be stored at room temperature of 2.5-3 bar. Can efficiently utilize the hydrogen storage material and improve the storage efficiency of the hydrogen.

Claims (4)

1. A solid hydrogen storage core is characterized in that the solid hydrogen storage core mainly comprises a core substrate, a transition layer and a hydrogen storage material layer, wherein the transition layer is positioned between the core substrate and the hydrogen storage material layer, and the hydrogen storage material layer is positioned on the surface of the solid hydrogen storage core;
the core body base material is a metal fiber felt, the material is 304 stainless steel, 316L stainless steel or 310S stainless steel, or an iron-chromium-aluminum metal material, the fiber diameter is 1-50 um, the porosity of the fiber felt is 70-90%, and the thickness of the fiber felt is 0.2-2 mm; the hydrogen storage material is LaNix (x = 1-5) or LaNixAl1-x(x =0.2 to 0.8); the thickness of the plating layer is 50-2000 nm; the transition layer is metal chromium or titanium, and the thickness is 10-1000 nm.
2. The method of making a solid state hydrogen storage core of claim 1, comprising the steps of:
(1) ion sputtering cleaning process
Ultrasonically cleaning a core body base material, drying the core body base material by using high-purity nitrogen, putting the core body base material into a non-equilibrium magnetron sputtering ion plating furnace chamber, heating to 50-300 ℃, and vacuumizing until the vacuum degree of the furnace chamber is lower than 3 multiplied by 10-3~6×10-3Pa, keeping the temperature for 0.5-5 h, and thenArgon is filled in, the vacuum degree of the furnace chamber is 0.2-2 Pa, bias voltage is applied to the substrate to be-200 to-1000V, the voltage of an ion source is applied to be 200-1000V, the surface of the substrate is bombarded by the ion source to remove the passive film, and the ion cleaning time is 10-120 min;
(2) depositing a transition layer
Starting a chromium target current, keeping the working air pressure between 0.2 Pa and 10Pa, keeping the bias voltage of the substrate between-50V and-800V, and depositing chromium on the surface of the core body for 1-20 min, wherein the chromium target current is 0.2-10A;
(3) depositing a hydrogen storage layer
The current of the chromium target is adjusted to 0, the bias voltage of the matrix is between 50 ℃ below zero and 800V, and the LaNixMaintaining the target current at 0.3-10A, and depositing for 2-200 min; depositing LaNi on the surface of the pure chromium layer prepared in the step (2)xAnd a hydrogen storage layer.
3. The method of making a solid state hydrogen storage core according to claim 2, wherein the step (2) of depositing the transition layer uses a titanium target.
4. The method of making a solid state hydrogen storage core according to claim 2, wherein said step (3) of depositing LaNixAl1-xThe hydrogen storage layer is specifically operated by adjusting the current of a chromium target to be 0, the bias voltage of a matrix to be-50 to-800V and LaNixThe target current is gradually reduced from 10A, the Al target is gradually increased from 0A, and the deposition lasts for 2-200 min;
or the Al target is gradually reduced from 5A, and LaNixThe target current is gradually increased from 0A, and the deposition time is 2-200 min; depositing LaNi on the surface of the pure chromium layer prepared in the step (2)xAl1-xAnd a hydrogen storage layer.
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CN113074317A (en) * 2021-03-22 2021-07-06 宁波瑞东技术转移有限公司 Dedicated integrated form hydrogen storage tank of hydrogen energy car

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JPS5827976A (en) * 1981-08-10 1983-02-18 Mitsubishi Chem Ind Ltd Hydrogen storage material
GB0317894D0 (en) * 2003-07-31 2003-09-03 Johnson Matthey Plc Hydrogen supply system
JP4828986B2 (en) * 2006-03-30 2011-11-30 株式会社東芝 Hydrogen storage alloy, hydrogen storage membrane and hydrogen storage tank
CN102220560A (en) * 2010-04-16 2011-10-19 湖北大学 Preparation method of LaNi5 film and application thereof
KR101439670B1 (en) * 2012-12-21 2014-09-17 주식회사 포스코 Method for manufacturing hydrogen storage alloy and hydrogen storage alloy using the same
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