CN110642626A - Ceramic material for sealing and protecting active metal high-temperature steam and preparation method thereof - Google Patents
Ceramic material for sealing and protecting active metal high-temperature steam and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an insulating ceramic material for sealing active metal high-temperature steam of Li, Na, K and the like, wherein the ceramic material comprises AlN and Si3N4BN, the active metals include Li, Na, K and the like. The preparation method of the material comprises the following steps: by using a hot-pressing sintering or field-assisted sintering mode and adding different sintering aids and optimizing a sintering process, the ceramic material for sealing active metal high-temperature steam such as Li, Na, K and the like is finally obtained, and the bending strength of the ceramic material is more than 300MPa, helium leakage rate < 1X 10‑ 10Pa·m3(s) volume resistivity > 1X 1010Omega cm, and the use temperature is 0-1000 ℃. The nitride ceramic material is applied to sealing and protection of the high-temperature battery for the first time, has the advantages of simple process, low cost, strong practicability and the like, and can effectively prolong the service life of the high-temperature battery.
Description
Technical Field
The invention belongs to the field of sealing materials, and particularly relates to a ceramic material for sealing active metal high-temperature steam such as Li, Na, K and the like and a preparation method thereof.
Technical Field
Energy, resources and environment are three major factors for the development of human society. With the development of social science and technology and the improvement of productivity, the energy problem is increasingly becoming a bottleneck restricting the sustainable development of socioeconomic. The efficient utilization of renewable clean energy such as solar energy and wind energy for power generation is a fundamental way for human beings to deal with the increasingly prominent energy crisis and the problem of pollution of traditional fossil fuels to the ecological environment, however, solar energy and wind energy belong to intermittent energy sources and have the problems of instability, discontinuity, great seasonal variation and the like, so that the network access efficiency is low and the stability of a power grid is affected, therefore, the development of a large-scale energy storage key technology is an inevitable trend for power grid development in the future, the peak clipping and valley filling of power are realized, and the power demand response capability is improved. Among many energy storage technologies, energy storage batteries have the advantages of no pollution in operation, high energy efficiency, long service life and the like, and in particular, electrochemical energy storage devices such as sodium-sulfur batteries, flow batteries and liquid metal batteries based on liquid design have high energy density and fast response time, and become a research hotspot in recent years.
The energy storage battery based on liquid state design is operated under the high temperature environment, and a proper high-temperature sealing technology is very important for the energy storage battery, so that the good sealing technology can not only ensure the energy storage quality of the battery, avoid the consumption of air and water on key active materials of the battery, prolong the service life of the battery, but also greatly reduce the later maintenance and operation cost of the operation of the battery. At a higher operation temperature (300 ℃), active metals such as Li, Na, K and the like of the negative electrode material of the energy storage battery are gradually converted into a high-temperature steam state, and the sealing difficulty of the battery is further improved. Aiming at the selection of key materials for packaging high-temperature energy storage batteries, related researches are carried out in the countries such as the United states, Europe and the like. For example, the AMBRI company in the United states adopts oxide ceramics as a sealing and insulating material of a liquid metal battery, the liquid metal battery produced in the first batch is respectively used for wind power energy storage in military bases of the Massachusetts in the United states and wind power energy storage in Hawaii islands, and the oxide ceramics can not realize long-term sealing and insulation; the university of Italian Diels in Europe developed silica-based glass ceramic sealing materials that did not exhibit significant chemical reaction and corrosion failure when operated at 300 ℃ for 250 hours; the glass ceramic sealed solid oxide fuel cell adopted by Ural high-temperature electrochemical research institute of Russian academy of sciences has a coefficient of thermal expansion equivalent to that of YSZ, and a fully sealed cell structure is obtained after 200 times of cold and heat cycles at 800-900 ℃.
At present, researches on active metal high-temperature steam sealing materials such as Li, Na, K and the like in an energy storage battery mainly focus on glass ceramic system sealing materials and oxide sealing materials, but glass ceramics have high brittleness and are easy to crack below the transition temperature; both glass and glass-ceramics contain alkali metal elements which react with other components in the battery to cause performance degradation; meanwhile, the oxide material is easy to react with active metal vapor under the working environment of the high-temperature battery, so that the sealing performance is reduced or the battery sealing is invalid.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: aiming at the strong corrosion working environment of active metal high-temperature steam such as Li, Na, K and the like, a ceramic material with strong high-temperature stability, corrosion resistance and insulating sealing property and a preparation method thereof are provided, and the problem of device failure caused by leakage of the active metal steam is avoided.
The invention adopts the following technical scheme for solving the technical problems:
the ceramic material for sealing the high-temperature steam of active metals such as Li, Na, K and the like provided by the invention comprises AlN and Si as raw materials3N4BN, the particle size of the raw material is in the size scale ofOn the order of microns.
The active metal vapor of the present invention includes Li, Na, K, etc.
The invention relates to a ceramic material for sealing active metal high-temperature steam such as Li, Na, K and the like.
In the above method, the hot pressing sintering method comprises the following steps:
(1) putting ceramic powder and a sintering aid into a ball mill, ball-milling for 2-4 h, and then putting into a drying oven to dry for 12h, wherein the drying temperature is 80 ℃;
(2) putting the dried ceramic powder into a graphite die with the diameter of 10-30 mm, and performing prepressing molding on the ceramic powder under the pressure of 5-10 MPa by using a tablet press;
(3) the ceramic material is prepared by hot-pressing sintering, and the sintering process comprises the following steps: the sintering temperature is 1400-1800 ℃, the heating rate is 1-10 ℃/min, the pressure is 10-50 MPa, the heat preservation time is 1-5 h, and the sintering atmosphere is nitrogen or argon.
In the above method, the field-assisted sintering method comprises the following steps:
(1) putting ceramic powder and a sintering aid into a ball mill, ball-milling for 2-4 h, and then putting into a drying oven to dry for 12h, wherein the drying temperature is 80 ℃;
(2) putting the dried ceramic powder into a graphite die with the diameter of 10-30 mm, and performing prepressing molding on the ceramic powder under the pressure of 5-10 MPa by using a tablet press;
(3) the ceramic material is prepared by hot-pressing sintering, and the sintering process comprises the following steps: the sintering temperature is 1400-1800 ℃, the heating rate is 50-200 ℃/min, the pressure is 10-50 MPa, the heat preservation time is 5-10 min, and the sintering atmosphere is nitrogen or argon.
In the above preparation method, the sintering aid used comprises Y2O3、Li2O, MgO, and the particle size is 1-5 μm.
The helium leakage rate of the ceramic material prepared by the invention for sealing the high-temperature steam of active metals such as Li, Na, K and the like is less than 1 multiplied by 10-10Pa·m3(s), bending strength >300 MPa, volume resistivity > 1X 1010Omega cm, sealing environment temperature 0-1000 deg.c.
Compared with the prior art, the invention has the following main advantages:
the research of the method and the material for sealing and protecting the active metal high-temperature vapor is less, the atomic numbers of Li, Na, K and the like are low, the radius is small, and the metal high-temperature vapor is difficult to seal. In addition, some special scenes also require that the sealing material has good insulation property, high temperature resistance and the like. Ceramic is the best candidate material for this sealing scenario. The conventional oxide ceramics and carbide are difficult to meet the requirements due to the reaction with metal vapor or poor insulation. The innovation point of the invention is that aiming at special sealing scenes of active metal steam such as Li, Na, K and the like, nitride ceramics are adopted as sealing materials, and two preparation methods of the nitride ceramics are described.
Aiming at special sealing scenes such as active metal steam of Li, Na, K and the like, nitride ceramics are used as a sealing key material of the high-temperature energy storage battery for the first time. The nitride ceramic has good thermodynamic stability and electrochemical stability, has good high-temperature stability with active metal vapor such as Li, Na, K and the like, effectively avoids the problem of sealing failure caused by the problems of aging, chemical reaction, structural damage and the like of the traditional high-temperature battery sealing materials (organic sealing glue, oxide ceramic sealing materials and glass ceramic sealing materials), has certain mechanical strength and volume resistivity, effectively isolates the positive and negative electrodes of the battery, avoids the problems of short circuit and the like during the operation of the battery, improves the cycle efficiency and prolongs the service life of the battery.
Meanwhile, the nitride ceramic has certain processability, the battery sealing structure can be subjected to corresponding structural design according to requirements in practical application, and finally, the nitride ceramic with the corresponding shape is obtained by processing according to requirements.
In conclusion, the nitride ceramic material is applied to the high-temperature battery for the first time, and compared with the existing sealing material, the nitride ceramic has higher stability and corrosion resistance; meanwhile, the invention also relates to a sintering method of the nitride ceramic, the nitride ceramic material with the performance meeting the requirements can be obtained by utilizing different sintering modes, the preparation method is simple, the cost is low, the service life of the high-temperature battery can be effectively prolonged by combining the nitride sealing material provided by the invention, and the industrialization of the novel high-temperature energy storage battery is promoted.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a diagram of a high temperature cell nitride sealing ceramic sample in accordance with the present invention;
FIG. 3 shows the use of different amounts of Y according to the invention2O3When sintering the auxiliary agent, the displacement curve of the aluminum nitride ceramic in the field-assisted sintering process changes with the temperature, wherein: 1# is pure AlN ceramic; 2# is AlN ceramic doped with 2 wt.% Y2O3(ii) a 3# is AlN ceramic doped with 3 wt.% Y2O3(ii) a 4# is AlN ceramic doped with 4 wt.% Y2O3；
FIG. 4 is an SEM image of a cross section of a nitride ceramic according to the present invention, wherein: graph a is the incorporation of 4 wt.% Y into AlN ceramic2O3Sintering auxiliary agent, wherein the sintering temperature is 1600 ℃; b, adding 5 wt.% of MgO sintering aid into AlN ceramic, wherein the sintering temperature is 1550 ℃; c, doping 20 wt.% BN powder into AlN ceramic, and sintering at 1700 ℃; d is at Si3N4Ceramic, sintering temperature 1450 ℃;
in the figure: 1. nitride ceramic, 2 stainless steel, 3 electrode current collector.
Detailed Description
The invention relates to a ceramic material for sealing active metal high-temperature steam of Li, Na, K and the like, wherein the ceramic material comprises AlN and Si3N4One or more of BN, active metal including one of Li, Na and K, etc, micron size of raw material, and micron powder material Y2O3、Li2O, MgO as a sintering aid. The ceramic material with excellent performance is finally obtained by controlling the sintering temperature to be 1400-1800 ℃, the heating rate to be 1-200 ℃/min and the sintering pressure to be 10-50 MPa. The raw materials used by the invention have wide sourcesAnd the preparation process is simple, and the prepared nitride ceramic material has strong high-temperature stability, corrosion resistance and insulating and sealing performance, and effectively realizes Li and Na active metal high-temperature vapor sealing.
The invention is further illustrated but not limited by the following examples and the accompanying drawings.
Example 1:
according to the AlN powder and the sintering aid Y2O3Weighing proper amount of AlN and Y according to the proportion of 97:3 in percentage by mass2O3The average grain diameter of the powder is 2 mu m, and the powder is put into a drying oven at 80 ℃ for drying for 12 hours after being ball milled for 3 hours by a ball mill. The ball mill used Retsch PM100, the same below.
The ball milling process comprises the following steps: putting the raw material powder into a 125ml nylon ball milling tank, and mixing the raw material powder: alcohol: ZrO (ZrO)2Ball milling is carried out according to the mass ratio of 1:1:4, and the ball mill is set to stop for 2min every 10 min.
Weighing 8g of the mixed powder, and paving the powder into a graphite mold with the inner diameter of 25mm, as shown in figure 1; and pre-pressing the sample for 30s under the pressure of 6MPa, and then carrying out field-assisted sintering.
The field-assisted sintering is selected under the nitrogen atmosphere, and the specific sintering process comprises the following steps: the sintering temperature is 1500 ℃, the heating rate is 100 ℃/min, the heat preservation time is 5min, the axial pressure is 30MPa, and the obtained helium leakage rate is 4.8 multiplied by 10-10Pa·m3(s), a bending strength of 250MPa, and a volume resistivity of 3.68X 1011An omega cm AlN ceramic sealing material.
Example 2:
according to AlN powder, sintering aids MgO and Y2O3Weighing proper amount of AlN, MgO and Y according to the weight percentage of 94:3:32O3The average grain diameter of the powder is 2 mu m, and the powder is put into a drying oven at 80 ℃ for drying for 12 hours after being ball milled for 3 hours by a ball mill.
The ball milling process comprises the following steps: putting the raw material powder into a 125ml nylon ball milling tank, and mixing the raw material powder: alcohol: ZrO (ZrO)2Ball milling is carried out according to the mass ratio of 1:1:4, and the ball mill is set to stop for 2min every 10 min.
Weighing 8g of mixed powder, paving the mixed powder into a graphite die with the inner diameter of 25mm, prepressing the sample under the pressure of 6MPa for 30s, and then carrying out hot-pressing sintering.
Hot-pressing sintering is selected under nitrogen atmosphere, and the specific sintering process comprises the following steps: the sintering temperature is 1550 ℃, the heating rate is 10 ℃/min, the heat preservation time is 120min, the axial pressure is 30MPa, and the obtained helium leakage rate is 2.7 multiplied by 10-11Pa·m3(s), bending strength 430MPa, volume resistivity 4.0X 1013An omega cm AlN ceramic sealing material.
Example 3:
according to the AlN powder, the BN powder and the sintering aid Y2O3Weighing proper amount of AlN, BN and Y according to the mass percent of 82.4:14.6:32O3The average grain diameter of the powder is 2 mu m, and the powder is put into a drying oven at 80 ℃ for drying for 12 hours after being ball milled for 3 hours by a ball mill.
The ball milling process comprises the following steps: putting the raw material powder into a 125ml nylon ball milling tank, and mixing the raw material powder: alcohol: ZrO (ZrO)2Ball milling is carried out according to the mass ratio of 1:1:4, and the ball mill is set to stop for 2min every 10 min.
Weighing 8g of mixed powder, paving the mixed powder into a graphite die with the inner diameter of 25mm, prepressing the sample under the pressure of 6MPa for 30s, and then carrying out hot-pressing sintering.
Hot-pressing sintering is selected under nitrogen atmosphere, and the specific sintering process comprises the following steps: the sintering temperature is 1600 ℃, the heating rate is 10 ℃/min, the heat preservation time is 120min, the axial pressure is 30MPa, and the obtained helium leakage rate is 1.2 multiplied by 10-10Pa·m3(s), a bending strength of 250MPa, and a volume resistivity of 3.68X 1011An AlN-BN ceramic sealing material of omega cm.
Example 4:
according to Si3N4Powder and sintering aid Y2O3Weighing proper amount of raw materials according to the mass ratio of 92:8, wherein Si is used3N4、Y2O3The average grain diameter of the powder is 2 mu m, and the powder is put into a drying oven at 80 ℃ for drying for 12 hours after being ball milled for 3 hours by a ball mill.
The ball milling process comprises the following steps: putting the raw material powder into a 125ml nylon ball milling tank, and mixing the raw material powder: alcohol：ZrO2Ball milling is carried out according to the mass ratio of 1:1:4, and the ball mill is set to stop for 2min every 10 min.
Weighing 8g of mixed powder, paving the mixed powder into a graphite die with the inner diameter of 25mm, prepressing the sample for 30s under the pressure of 6MPa, and then carrying out field-assisted sintering.
The field-assisted sintering is selected under the nitrogen atmosphere, and the specific sintering process comprises the following steps: the sintering temperature is 1450 ℃, the heating rate is 100 ℃/min, the heat preservation time is 5min, the axial pressure is 30MPa, and the obtained helium leakage rate is 1.4 multiplied by 10-11Pa·m3(s) a flexural strength of 370MPa and a volume resistivity of 1.5X 1013Omega cm of Si3N4A ceramic sealing material.
Claims (10)
1. A ceramic material for sealing and protecting active metal high-temperature steam is characterized in that the active metal comprises one of Li, Na and K, and the ceramic material is AlN and Si3N4And one or more of BN and micron-sized ceramic raw material grain size.
2. The active metal high-temperature vapor sealing and protecting ceramic material as claimed in claim 1, wherein the grain size of the ceramic raw material is 1-5 μm.
3. The active metal high temperature vapor sealing and shielding ceramic material of claim 1, wherein said active metal is replaced with metallic Mg.
4. A method for preparing ceramic material for sealing and protecting active metal high-temperature steam is characterized in that a hot-pressing sintering or field-assisted sintering mode is utilized, micron powder sintering aid is added, and hot-pressing sintering is carried out under nitrogen or argon to obtain the ceramic material mainly used for sealing Li, Na or K active metal high-temperature steam, wherein the ceramic material is AlN, Si or K active metal high-temperature steam3N4And one or more of BN and micron-sized ceramic raw material grain size.
5. The method according to claim 4, wherein the hot press sintering comprises the steps of:
(1) putting ceramic powder and a sintering aid into a ball mill, ball-milling for 2-4 h, and then putting into a drying oven to dry for 12h, wherein the drying temperature is 80 ℃;
(2) putting the dried ceramic powder into a graphite die with the diameter of 10-30 mm, and performing prepressing molding on the ceramic powder under the pressure of 5-10 MPa by using a tablet press;
(3) the ceramic material is prepared by hot-pressing sintering, and the sintering process comprises the following steps: the sintering temperature is 1400-1800 ℃, the heating rate is 1-10 ℃/min, the pressure is 10-50 MPa, the heat preservation time is 1-5 h, and the sintering atmosphere is nitrogen or argon.
6. The method according to claim 4, wherein the field-assisted sintering method comprises the following steps:
(1) putting ceramic powder and a sintering aid into a ball mill, ball-milling for 2-4 h, and then putting into a drying oven to dry for 12h, wherein the drying temperature is 80 ℃;
(2) putting the dried ceramic powder into a graphite die with the diameter of 10-30 mm, and performing prepressing molding on the ceramic powder under the pressure of 5-10 MPa by using a tablet press;
(3) the field-assisted sintering is utilized to prepare the ceramic material, and the sintering process comprises the following steps: the sintering temperature is 1400-1800 ℃, the heating rate is 50-200 ℃/min, the pressure is 10-50 MPa, the heat preservation time is 5-10 min, and the sintering atmosphere is nitrogen or argon.
7. The method according to claim 4, wherein the sintering aid comprises Y2O3、Li2O, MgO, the particle size of the sintering aid raw material is 1-5 μm.
8. The method according to any one of claims 4 to 7, wherein the ceramic material has a helium leak rate of less than 1 x 10-10Pa·m3(s), bending strength >300 MPa, volume resistivity > 1X 1010Omega cm, sealing environment temperature 0-1000 deg.c.
9. The active metal high temperature vapor sealing and shielding ceramic material prepared by the method of claim 8, which is used in a high temperature battery.
10. The active metal high-temperature vapor sealing and protecting ceramic material as claimed in any one of claims 1 to 3, which is used in a high-temperature battery.
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| CN201911029564.7A CN110642626A (en) | 2019-10-28 | 2019-10-28 | Ceramic material for sealing and protecting active metal high-temperature steam and preparation method thereof |
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| CN112047739A (en) * | 2020-07-23 | 2020-12-08 | 全球能源互联网研究院有限公司 | Processable ceramic/metal gradient structure material and preparation method thereof |
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| US4382117A (en) * | 1978-11-02 | 1983-05-03 | Varta Batterie Aktiengesellschaft | Separator for electrochemical high temperature cell |
| CN106711382A (en) * | 2017-02-10 | 2017-05-24 | 武汉理工大学 | Non-oxide porous diaphragm material for high-temperature batteries and preparation method thereof |
| CN108620594A (en) * | 2018-04-26 | 2018-10-09 | 武汉理工大学 | A kind of ceramic/metal gradient-structure High-temperature Packaging material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4382117A (en) * | 1978-11-02 | 1983-05-03 | Varta Batterie Aktiengesellschaft | Separator for electrochemical high temperature cell |
| CN106711382A (en) * | 2017-02-10 | 2017-05-24 | 武汉理工大学 | Non-oxide porous diaphragm material for high-temperature batteries and preparation method thereof |
| CN108620594A (en) * | 2018-04-26 | 2018-10-09 | 武汉理工大学 | A kind of ceramic/metal gradient-structure High-temperature Packaging material and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112047739A (en) * | 2020-07-23 | 2020-12-08 | 全球能源互联网研究院有限公司 | Processable ceramic/metal gradient structure material and preparation method thereof |
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