CN103303971B - One Ti 4o 7it is the method that powder prepares electrode material - Google Patents

One Ti 4o 7it is the method that powder prepares electrode material Download PDF

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CN103303971B
CN103303971B CN201310252646.4A CN201310252646A CN103303971B CN 103303971 B CN103303971 B CN 103303971B CN 201310252646 A CN201310252646 A CN 201310252646A CN 103303971 B CN103303971 B CN 103303971B
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powder
electrode material
sintering
mould
furnace
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CN103303971A (en
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刘颖
叶金文
张晓燕
朱瑞杰
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Sichuan University
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Sichuan University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

One Ti 4o 7be the method that powder prepares electrode material, by Ti 4o 7be that powder loads mould, and Ti will be housed 4o 7be that the mould of powder puts into sintering furnace, 0 ~ 1 × 10 -3to the Ti in mould under the vacuum condition of Pa 4o 7be that powder pressing is warming up to 500 ~ 900 DEG C of sintering 5 ~ 15min, cool to less than 100 DEG C after terminating with the furnace and come out of the stove, namely obtain electrode material, described Ti 4o 7be that powder loads the amount of mould and is limited with the heap(ed) capacity being no more than mould, in described intensification, sintering and temperature-fall period, institute's plus-pressure is 10 ~ 20KN, and keeps same pressure in intensification, sintering and temperature-fall period.<!--1-->

Description

One Ti 4o 7it is the method that powder prepares electrode material
Technical field
The invention belongs to electrode material preparation field, particularly one Ti 4o 7it is the method that powder prepares electrode material.
Background technology
Ti 4o 7be that powder refers to Ti 4o 7powder and at Ti 4o 7the powder that on basis, doped metallic elements is formed, because it has high conductivity, acid-fast alkali-proof, can be used for preparing the electrode material in lithium battery, lithium-empty battery and fuel cell equal energy source field.During practical application, be by Ti 4o 7be powder be processed into have certain degree of hardness and intensity sheet or bulk material.In prior art, by Ti 4o 7being the common method that powder is processed into sheet or bulk material is: by Ti 4o 7be that powder mixes rear loading mould, at room temperature extrusion forming, heat drying after the demoulding with adhesive solution.And the interpolation of bonding agent causes compressing electrode material electrical conductance to weaken, limit its application as conductive electrode film.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, one Ti is provided 4o 7be the method that powder prepares electrode material, to improve the conductivity of prepared electrode material, and make it have high density.
Technical scheme of the present invention: do not add high polymer binder, directly by Ti 4o 7be that powder loads mould, pressurization is warming up to 500 ~ 900 DEG C and sinters under vacuum.
Ti of the present invention 4o 7be the method that powder prepares electrode material, its Ti 4o 7be the chemical formula of powder be (Ti 1-x, M x) 4o 7, in formula, 0≤x≤0.5, M is doped metallic elements, and processing step is as follows:
By Ti 4o 7be that powder loads mould, and Ti will be housed 4o 7be that the mould of powder puts into sintering furnace, 0 ~ 1 × 10 -3to the Ti in mould under the vacuum condition of Pa 4o 7be that powder pressing is warming up to 500 ~ 900 DEG C of sintering 5 ~ 15min, cool to less than 100 DEG C after terminating with the furnace and come out of the stove, namely obtain electrode material, described Ti 4o 7be that powder loads the amount of mould and is limited with the heap(ed) capacity being no more than mould, in described intensification, sintering and temperature-fall period, institute's plus-pressure is 10 ~ 20KN, and keeps same pressure in intensification, sintering and temperature-fall period.
Above-mentioned Ti 4o 7be the method that powder prepares electrode material, described M is at least one in metallic element V, Nb, W of+5 valencys.
Above-mentioned Ti 4o 7be the method that powder prepares electrode material, described sintering furnace is the one in discharge plasma sintering stove, hot-pressed sintering furnace, electric field activation pressure assisted sintering stove.
Above-mentioned Ti 4o 7be the method that powder prepares electrode material, described mould is the one in graphite jig, sintered-carbide die, steel die.
Ti 4o 7it is the doped Ti in powder 4o 7raw powder's production technology is as follows:
(1) prepare burden
Raw material is titanium source, metallic element M source, carbonaceous reducing agent or titanium matter reducing agent, according to doped Ti 4o 7the chemical formula of powder and raw materials used between chemical reaction measure each raw material, described doped Ti 4o 7the chemical formula of powder is (Ti 1-x, M x) 4o 7, in described chemical formula, M is doped metallic elements, 0 ﹤ x≤0.5;
(2) batch mixing is dry
The raw material that step (1) measures is put into ball mill and carries out wet-milling dispersion, raw material is mixed, then sieving separating goes out to grind spheroid and obtains mixed slurry, described mixed slurry is carried out dry sintering raw mix;
(3) sinter
Sintering raw mix prepared by step (2) under vacuum or nitrogen or argon gas atmosphere in 850 DEG C ~ 1350 DEG C sintering 1 hour ~ 4 hours, continue after cool to less than 100 DEG C with the furnace and come out of the stove, namely obtain doped Ti 4o 7powder.
Above-mentioned doped Ti 4o 7raw powder's production technology, described titanium source is TiO 2powder, metallic element M source is at least one in the pentavalent oxide powder of V, Nb, W.
Above-mentioned doped Ti 4o 7raw powder's production technology, described carbonaceous reducing agent is any one in carbon powder, graphite powder, activated carbon powder, charcoal powder, glucose, and described titanium matter reducing agent is titanium valve or hydride powder.
Above-mentioned doped Ti 4o 7raw powder's production technology, the baking temperature of mixed slurry is 50 DEG C ~ 100 DEG C, and drying time is 2 hours ~ 6 hours.
Compared with prior art, the present invention has following beneficial effect:
1, due to Ti of the present invention 4o 7be that powder is prepared in the method for electrode material and do not added any bonding agent, thus the conductivity of obtained electrode material increases substantially (see each embodiment, comparative example), ensure that its application demand as electrode and electric conducting material.
2, experiment shows, electrode material density prepared by the method for the invention is high, and its relative density can reach more than 94% (see each embodiment).
3, the method for the invention technique is simple, and preparation time shortens compared with the conventional method, is conducive to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is Ti prepared by embodiment 1 4o 7the optical photograph of electrode material.
Fig. 2 is Ti prepared by embodiment 1 4o 7the X-ray diffractogram of electrode material.
Fig. 3 is Ti prepared by embodiment 1 4o 7the scanning electron microscope (SEM) photograph of electrode material.
Embodiment
Below by embodiment to Ti of the present invention 4o 7be that the method that powder prepares electrode material is described further.
In following embodiment, the conductivity of electrode material adopts identical four-point probe to test, and density adopts drainage test, and relative density is with Ti 4o 7solid density (4.32g/cm 2) based on calculate.
In following embodiment, described material powder all can be bought from market.The model of discharge plasma sintering stove is SPS-1050, and Amada Co., Ltd. produces; The model of hot-pressed sintering furnace is HP20-4560-20, and QuantumDesign company of the U.S. produces; The model of electric field activation pressure assisted sintering stove is Gleeble3500, and DSI company of the U.S. produces.
In following embodiment, described ratio of grinding media to material refers to the mass ratio of grinding spheroid and material in ball mill.
Embodiment 1
In the present embodiment, use Ti 4o 7powder prepares pellet electrode material, and processing step is as follows:
Choose the graphite jig that diameter is φ 20, place one deck carbon paper in a mold, and weigh 3.5gTi 4o 7powder puts into mould, then Ti will be housed 4o 7discharge plasma sintering stove put into by the mould of powder, and vacuumizes airtight for discharge plasma sintering stove, when the vacuum degree in stove is 1 × 10 -1during Pa, 900 DEG C of sintering 15min are warming up to powder pressing, cool to 80 DEG C after terminating with the furnace and come out of the stove, after moving back mould, namely obtain sheet Ti 4o 7electrode material (see figure 1), in described intensification, sintering and temperature-fall period, institute's plus-pressure is 10KN, and described heating rate is 90 DEG C/min.After tested, prepared sheet Ti 4o 7the conductivity of electrode material is 750S/cm, and density is 4.07g/cm 3, relative density is 94.2%, prepared sheet Ti 4o 7the X-ray diffractogram of electrode material is shown in Fig. 2, prepared sheet Ti 4o 7the scanning electron microscope (SEM) photograph of electrode material is shown in Fig. 3.As can be seen from Figure 2, the electrode material prepared through oversintering is still by single Ti 4o 7phase composition; As can be seen from Figure 3, electrode material has formed fine and close sintered body, and crystal grain is tiny and even.
Comparative example:
0.35g epoxy resin is dissolved in 2ml acetone, then adds 3.5gTi 4o 7powder also mixes, continue after mixed material is loaded in mould, at room temperature apply 10KN pressure and pressurize 1 minute, pressurize terminated the rear demoulding and takes out shaping sheet electrode material and put into baking oven, normal pressure, 50 DEG C of dryings 30 minutes.After tested, the conductivity of prepared electrode material is 250S/cm.
As can be seen from above-described embodiment, comparative example, under identical briquetting pressure, Ti prepared by the inventive method 4o 7ti prepared by electrode material and existing method 4o 7electrode material is compared, and its conductivity about improves 200%.
Embodiment 2
In the present embodiment, with (Ti 0.5, V 0.5) 4o 7powder prepares pellet electrode material, and processing step is as follows successively:
(1) (Ti 0.5, V 0.5) 4o 7the preparation of powder
1. prepare burden
According to chemical formula (Ti 0.5, V 0.5) 4o 7and raw materials used between chemical reaction measure each raw material, the percentage by weight of each raw material is as follows:
Micron TiO 2powder 33.10wt%,
Micron V 2o 5powder 56.56wt%,
Micron titantium hydride powder 10.34wt%;
2. batch mixing is with dry
Tumbling ball mill put into by raw material step 1. measured, with diameter be φ 10mm WC-8wt%Co sintered carbide ball be grinding spheroid, ratio of grinding media to material is 8:1, take absolute ethyl alcohol as wet grinding media, its addition, to flood described raw material and grinding spheroid is limited, the lower grinding distribution of rotational speed of ball-mill 30 revs/min 75 hours, makes raw material mix, then sieving separating goes out to grind spheroid and obtains mixed slurry, described mixed slurry is placed in inherent 50 DEG C of dryings of baking oven 6 hours sintering raw mix;
3. powder sintering
Sintering raw mix step 2. prepared puts into pipe type sintering furnace, under the flowing Ar gas atmosphere of 200ml/min, is warming up to 1350 DEG C of sintering 1 hour, then cools to room temperature with the furnace, obtain (Ti 0.5, V 0.5) 4o 7powder, particle diameter is 1 ~ 5 μm.
(2) electrode material preparation
Choose the graphite jig that diameter is φ 20, place one deck carbon paper in a mold, and weigh 4g (Ti 0.5, V 0.5) 4o 7powder puts into mould, then (Ti will be housed 0.5, V 0.5) 4o 7hot-pressed sintering furnace put into by the mould of powder, and vacuumizes airtight for hot-pressed sintering furnace, when the vacuum degree in stove is 0Pa, is warming up to 850 DEG C of sintering 12min, cools to 80 DEG C with the furnace and come out of the stove, namely obtain sheet (Ti after moving back mould after terminating powder pressing 0.5, V 0.5) 4o 7electrode material, in described intensification, sintering and temperature-fall period, institute's plus-pressure is 16KN, and described heating rate is 80 DEG C/min.After tested, prepared sheet (Ti 0.5, V 0.5) 4o 7the conductivity of electrode material is 850S/cm, and density is 4.14g/cm 3, relative density is 95.8%.
Comparative example:
0.35g epoxy resin is dissolved in 2ml acetone, then adds 3.5g (Ti 0.5, V 0.5) 4o 7powder also mixes, continue after mixed material is loaded in mould, at room temperature apply 16KN pressure and pressurize 1 minute, pressurize terminated the rear demoulding and takes out shaping sheet electrode material and put into baking oven, normal pressure, 50 DEG C of dryings 30 minutes.After tested, the conductivity of prepared electrode material is 300S/cm.
As can be seen from above-described embodiment, comparative example, under identical briquetting pressure, (Ti prepared by the inventive method 0.5, V 0.5) 4o 7(Ti prepared by electrode material and existing method 0.5, V 0.5) 4o 7electrode material is compared, and its conductivity about improves 183%.
Embodiment 3
In the present embodiment, with (Ti 0.5, Nb 0.5) 4o 7powder prepares pellet electrode material, and processing step is as follows successively:
(1) (Ti 0.5, Nb 0.5) 4o 7the preparation of powder
1. prepare burden
According to chemical formula (Ti 0.5, Nb 0.5) 4o 7and raw materials used between chemical reaction measure each raw material, the percentage by weight of each raw material is as follows:
Micron TiO 2powder 35.53wt%,
Micron Nb 2o 5powder 59.13wt%,
Micron carbon black powder 5.34wt%;
2. batch mixing is with dry
Tumbling ball mill put into by raw material step 1. measured, with diameter be φ 10mm WC-8wt%Co sintered carbide ball be grinding spheroid, ratio of grinding media to material is 8:1, take absolute ethyl alcohol as wet grinding media, its addition, to flood described raw material and grinding spheroid is limited, the lower grinding distribution of rotational speed of ball-mill 20 revs/min 90 hours, makes raw material mix, then sieving separating goes out to grind spheroid and obtains mixed slurry, described mixed slurry is placed in inherent 60 DEG C of dryings of baking oven 4 hours sintering raw mix;
3. powder sintering
Sintering raw mix step 2. prepared puts into vacuum carbon tube furnace, and being evacuated to vacuum degree is 1 × 10 -1pa, is warming up to 1000 DEG C of sintering 3.5 hours, then cools to room temperature with the furnace, obtain (Ti 0.5, Nb 0.5) 4o 7powder, particle size range is 3-6 μm.
(2) electrode material preparation
Choose the graphite jig that diameter is φ 20, place one deck carbon paper in a mold, and weigh 4g (Ti 0.5, Nb 0.5) 4o 7powder puts into mould, then (Ti will be housed 0.5, Nb 0.5) 4o 7electric field activation pressure assisted sintering stove put into by the mould of powder, and vacuumizes airtight for electric field activation pressure assisted sintering stove, when the vacuum degree in stove is 2 × 10 -2during Pa, 800 DEG C of sintering 5min are warming up to powder pressing, cool to 80 DEG C after terminating with the furnace and come out of the stove, after moving back mould, namely obtain sheet (Ti 0.5, Nb 0.5) 4o 7electrode material, in described intensification, sintering and temperature-fall period, institute's plus-pressure is 20KN, and described heating rate is 80 DEG C/min.After tested, prepared sheet (Ti 0.5, Nb 0.5) 4o 7the conductivity of electrode material is 850S/cm, and density is 4.17g/cm 3. relative density is 96.5%.
Comparative example:
0.35g epoxy resin is dissolved in 2ml acetone, then adds 3.5g (Ti 0.5, Nb 0.5) 4o 7powder also mixes, continue after mixed material is loaded in mould, at room temperature apply 20KN pressure and pressurize 1 minute, pressurize terminated the rear demoulding and takes out shaping sheet electrode material and put into baking oven, normal pressure, 50 DEG C of dryings 30 minutes.After tested, the conductivity of prepared electrode material is 310S/cm.
As can be seen from above-described embodiment, comparative example, under identical briquetting pressure, (Ti prepared by the inventive method 0.5, Nb 0.5) 4o 7(Ti prepared by electrode material and existing method 0.5, Nb 0.5) 4o 7electrode material is compared, and its conductivity about improves 174%.
Embodiment 4
In the present embodiment, with (Ti 0.5, W 0.5) 4o 7powder prepares stick electrode material, and processing step is as follows successively:
(1) (Ti 0.5, W 0.5) 4o 7the preparation of powder
1. prepare burden
According to chemical formula (Ti 0.5, W 0.5) 4o 7and raw materials used between chemical reaction measure each raw material, the percentage by weight of each raw material is as follows:
Micron TiO 2powder 24.22wt%,
Micron WO 3powder 70.32wt%,
Micron carbon black powder 5.46wt%;
2. batch mixing is with dry
Tumbling ball mill put into by raw material step 1. measured, with diameter be φ 10mm WC-8wt%Co sintered carbide ball be grinding spheroid, ratio of grinding media to material is 8:1, take absolute ethyl alcohol as wet grinding media, its addition, to flood described raw material and grinding spheroid is limited, the lower grinding distribution of rotational speed of ball-mill 20 revs/min 80 hours, makes raw material mix, then sieving separating goes out to grind spheroid and obtains mixed slurry, described mixed slurry is placed in inherent 75 DEG C of dryings of baking oven 3 hours sintering raw mix;
3. powder sintering
Sintering raw mix step 2. prepared puts into pipe type sintering furnace, at the flowing N of 500ml/min 2under atmosphere, be warming up to 1100 DEG C of sintering 4 hours, then cool to room temperature with the furnace, obtain (Ti 0.5, W 0.5) 4o 7powder, particle size range is 3-6 μm.
(2) electrode material preparation
Choose the steel die that diameter is φ 13, place one deck carbon paper in a mold, and weigh 20g (Ti 0.5, W 0.5) 4o 7powder puts into mould, then (Ti will be housed 0.5, W 0.5) 4o 7discharge plasma sintering stove put into by the mould of powder, and vacuumizes airtight for discharge plasma sintering stove, when the vacuum degree in stove is 3 × 10 -3during Pa, 500 DEG C of sintering 10min are warming up to powder pressing, cool to 80 DEG C after terminating with the furnace and come out of the stove, after moving back mould, namely obtain sheet (Ti 0.5, W 0.5) 4o 7electrode material, in described intensification, sintering and temperature-fall period, institute's plus-pressure is 15KN, and described heating rate is 60 DEG C/min.After tested, prepared bar-shaped (Ti 0.5, W 0.5) 4o 7the conductivity of electrode material is 700S/cm, and density is 4.01g/cm 3, relative density is 92.8%.
Comparative example:
2g epoxy resin is dissolved in 20ml acetone, then adds 20g (Ti 0.5, W 0.5) 4o 7powder also mixes, continue after mixed material is loaded in mould, at room temperature apply 15KN pressure and pressurize 1 minute, pressurize terminated the rear demoulding and takes out shaping bar-shaped electrode material and put into baking oven, normal pressure, 50 DEG C of dryings 30 minutes.After tested, the conductivity of prepared electrode material is 280S/cm.
As can be seen from above-described embodiment, comparative example, under identical briquetting pressure, (Ti prepared by the inventive method 0.5, W 0.5) 4o 7(Ti prepared by electrode material and existing method 0.5, W 0.5) 4o 7electrode material is compared, and its conductivity about improves 150%.
Embodiment 5
In the present embodiment, with (Ti 0.5, V 0.5) 4o 7powder prepares pellet electrode material, and processing step is as follows successively
(1) (Ti 0.5, V 0.5) 4o 7the preparation of powder
1. prepare burden
According to chemical formula (Ti 0.5, V 0.5) 4o 7and raw materials used between chemical reaction measure each raw material, the percentage by weight of each raw material is as follows:
Micron TiO 2powder 33.10wt%,
Micron V 2o 5powder 56.56wt%,
Micron titantium hydride powder 10.34wt%;
2. batch mixing is with dry
Tumbling ball mill put into by raw material step 1. measured, with diameter be φ 10mm WC-8wt%Co sintered carbide ball be grinding spheroid, ratio of grinding media to material is 8:1, take absolute ethyl alcohol as wet grinding media, its addition, to flood described raw material and grinding spheroid is limited, the lower grinding distribution of rotational speed of ball-mill 30 revs/min 75 hours, makes raw material mix, then sieving separating goes out to grind spheroid and obtains mixed slurry, described mixed slurry is placed in inherent 50 DEG C of dryings of baking oven 6 hours sintering raw mix;
3. powder sintering
Sintering raw mix step 2. prepared puts into pipe type sintering furnace, under the flowing Ar gas atmosphere of 200ml/min, is warming up to 1350 DEG C of sintering 1 hour, then cools to room temperature with the furnace, obtain (Ti 0.5, V 0.5) 4o 7powder, particle diameter is 1-5 μm.
(2) electrode material preparation
Choose the sintered-carbide die that diameter is φ 20, place one deck carbon paper in a mold, and weigh 4g (Ti 0.5, V 0.5) 4o 7powder puts into mould, then (Ti will be housed 0.5, V 0.5) 4o 7hot-pressed sintering furnace put into by the mould of powder, and vacuumizes airtight for hot-pressed sintering furnace, when the vacuum degree in stove is 1 × 10 -3during Pa, 750 DEG C of sintering 10min are warming up to powder pressing, cool to 80 DEG C after terminating with the furnace and come out of the stove, after moving back mould, namely obtain sheet (Ti 0.5, V 0.5) 4o 7electrode material, in described intensification, sintering and temperature-fall period, institute's plus-pressure is 15KN, and described heating rate is 80 DEG C/min.After tested, prepared sheet (Ti 0.5, V 0.5) 4o 7the conductivity of electrode material is 810S/cm, and density is 4.15g/cm 3. relative density is 96.1%.
Comparative example:
0.35g epoxy resin is dissolved in 2ml acetone, then adds 3.5g (Ti 0.5, V 0.5) 4o 7powder also mixes, continue after mixed material is loaded in mould, at room temperature apply 15KN pressure and pressurize 1 minute, pressurize terminated the rear demoulding and takes out shaping sheet electrode material and put into baking oven, normal pressure, 50 DEG C of dryings 30 minutes.After tested, the conductivity of prepared electrode material is 270S/cm.
As can be seen from above-described embodiment, comparative example, under identical briquetting pressure, (Ti prepared by the inventive method 0.5, V 0.5) 4o 7(Ti prepared by electrode material and existing method 0.5, V 0.5) 4o 7electrode material is compared, and its conductivity about improves 200%.
Embodiment 6
In the present embodiment, with (Ti 0.5, Nb 0.2, V 0.2, W 0.1) 4o 7powder prepares pellet electrode material, and processing step is as follows successively
(1) (Ti 0.5, Nb 0.2, V 0.2, W 0.1) 4o 7the preparation of powder
1. prepare burden
According to chemical formula (Ti 0.5, Nb 0.2, V 0.2, W 0.1) 4o 7and raw materials used between chemical reaction measure each raw material, the percentage by weight of each raw material is as follows:
2. batch mixing is with dry
Tumbling ball mill put into by raw material step 1. measured, with diameter be φ 10mm WC-8wt%Co sintered carbide ball be grinding spheroid, ratio of grinding media to material is 8:1, take absolute ethyl alcohol as wet grinding media, its addition, to flood described raw material and grinding spheroid is limited, the lower grinding distribution of rotational speed of ball-mill 30 revs/min 80 hours, makes raw material mix, then sieving separating goes out to grind spheroid and obtains mixed slurry, described mixed slurry is placed in inherent 70 DEG C of dryings of baking oven 2.5 hours sintering raw mix;
3. sinter
Sintering raw mix step 2. prepared puts into pipe type sintering furnace, under the flowing Ar atmosphere of 200ml/min, is warming up to 1080 DEG C of sintering 3 hours, then cools to room temperature with the furnace, obtain (Ti 0.5, Nb 0.2, V 0.2, W 0.1) 4o 7powder, particle size range is 3-5 μm.
(2) electrode material preparation
Choose the sintered-carbide die that diameter is φ 30, place one deck carbon paper in a mold, and weigh 4g (Ti 0.5, Nb 0.2, V 0.2, W 0.1) 4o 7powder puts into mould, then (Ti will be housed 0.5, Nb 0.2, V 0.2, W 0.1) 4o 7hot-pressed sintering furnace put into by the mould of powder, and vacuumizes airtight for hot-pressed sintering furnace, when the vacuum degree in stove is 8 × 10 -2during Pa, 700 DEG C of sintering 12min are warming up to powder pressing, cool to 80 DEG C after terminating with the furnace and come out of the stove, after moving back mould, namely obtain sheet (Ti 0.5, V 0.5) 4o 7electrode material, in described intensification, sintering and temperature-fall period, institute's plus-pressure is 14KN, and described heating rate is 60 DEG C/min.After tested, prepared sheet (Ti 0.5, Nb 0.2, V 0.2, W 0.1) 4o 7the conductivity of electrode material is 800S/cm, and density is 4.10g/cm 3, relative density is 94.9%.
Comparative example:
0.35g epoxy resin is dissolved in 2ml acetone, then adds 3.5g (Ti 0.5, Nb 0.2, V 0.2, W 0.1) 4o 7powder also mixes, continue after mixed material is loaded in mould, at room temperature apply 14KN pressure and pressurize 1 minute, pressurize terminated the rear demoulding and takes out shaping sheet electrode material and put into baking oven, normal pressure, 50 DEG C of dryings 30 minutes.After tested, the conductivity of prepared electrode material is 286S/cm.
As can be seen from above-described embodiment, comparative example, under identical briquetting pressure, (Ti prepared by the inventive method 0.5, Nb 0.2, V 0.2, W 0.1) 4o 7(Ti prepared by electrode material and existing method 0.5, Nb 0.2, V 0.2, W 0.1) 4o 7electrode material is compared, and its conductivity about improves 180%.

Claims (5)

1. one kind with Ti 4o 7be the method that powder prepares electrode material, described Ti 4o 7be the chemical formula of powder be (Ti 1-x,m x) 4o 7, wherein 0≤x≤0.5, M is doped metallic elements, it is characterized in that processing step is as follows:
By Ti 4o 7be that powder loads mould, and Ti will be housed 4o 7be that the mould of powder puts into sintering furnace, 0 ~ 1 × 10 -3to the Ti in mould under the vacuum condition of Pa 4o 7be that powder pressing is warming up to 700 ~ 900 DEG C of sintering 5 ~ 15min, cool to less than 100 DEG C after terminating with the furnace and come out of the stove, namely obtain electrode material, described Ti 4o 7be that powder loads the amount of mould and is limited with the heap(ed) capacity being no more than mould, in described intensification, sintering and temperature-fall period, institute's plus-pressure is 10 ~ 20KN, and keeps same pressure in intensification, sintering and temperature-fall period.
2. use Ti according to claim 1 4o 7be the method that powder prepares electrode material, it is characterized in that described M is at least one in metallic element V, Nb, W of+5 valencys.
3. according to claim 1 or 2, use Ti 4o 7be the method that powder prepares electrode material, it is characterized in that described sintering furnace is the one in discharge plasma sintering stove, hot-pressed sintering furnace, electric field activation pressure assisted sintering stove.
4. according to claim 1 or 2, use Ti 4o 7be the method that powder prepares electrode material, it is characterized in that described mould is the one in graphite jig, sintered-carbide die, steel die.
5. use Ti according to claim 3 4o 7be the method that powder prepares electrode material, it is characterized in that described mould is the one in graphite jig, sintered-carbide die, steel die.
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