CN100392894C - A cathode material for direct carbon fuel cell and its manufacture method - Google Patents
A cathode material for direct carbon fuel cell and its manufacture method Download PDFInfo
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- CN100392894C CN100392894C CNB2005101177391A CN200510117739A CN100392894C CN 100392894 C CN100392894 C CN 100392894C CN B2005101177391 A CNB2005101177391 A CN B2005101177391A CN 200510117739 A CN200510117739 A CN 200510117739A CN 100392894 C CN100392894 C CN 100392894C
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- cathode material
- direct carbon
- consuming cell
- carbon consuming
- dcfc
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The rare earth oxide composite cathode material for direct carbon fuel battery comprises following ingredients as mole percent content: 50-90% Ni, 1-18% Gd2O3, 1-20% CeO2, 0.5-7% La2O3, 1-7% Nd2O3, 0.5-7% Yb2O3, 1-4% ZrO2, and 1-4% MgO. This invention can increase the power density and current density of fuel battery, and reduces battery working temperature.
Description
Technical field
The invention belongs to the fuel cell material technical field, particularly direct carbon consuming cell cathode material and preparation method thereof.
Background technology
Directly carbon consuming cell (Direct Carbon Fuel Cell) has energy conversion efficiency height, environmental friendliness (no Sox, NOx discharging, noiselessness pollutes), the wide outstanding advantages such as (can directly use the various carbon containing fossil fuels such as derivative of coal, coal) of fuel tolerance.Compare with the traditional hot machine, directly carbon consuming cell can improve coal and the transformation efficiency of various carbon containing fossil fuels in Conversion of energy, farthest carbon containing fossil fuel chemical energy is converted into electric energy.
Relevant patent of DCFC and research contents focus mostly at aspects such as DCFC internal structure, electrolyte compositional optimization, electrode material improvement in the world at present.United States Patent (USP) 555511 in 1896, use fusion NaOH and KOH to do electrolyte, pure iron and coke are done electrode, 500 ℃ of working temperatures, this patent proposes the notion and the prototype of direct carbon consuming cell the earliest, proposes to add basic anhydride to solve the rotten problem of aging of electrolyte in electrolyte.The subject matter of this patent is that DCFC power density and current density are lower.United States Patent (USP) 3970474 in 1976 uses fused carbonate to do electrolyte, and motlten metal lead, bismuth, antimony mix as anode material with carbon, and this DCFC is when 805 ℃ of work, and maximum power density is 21 mW/cm
2The subject matter of DCFC is the working temperature height in this patent, electrode and battery structure spare seriously corroded, and fuel battery power density and current density are lower.The United States Patent (USP) 6200697 of calendar year 2001 uses graphite, stainless steel to do electrode, and the molten caustic soda mixture is done electrolyte, adds other basic anhydride simultaneously to solve the electrolyte spoilage problems.The DCFC working temperature is 400 ℃ in this patent, open circuit voltage (Open circuit voltage) 0.715V, maximum current density 98mA/cm
2, this patent proposes a kind of DCFC structure and a kind of rotten method of electrolyte that solves.United States Patent (USP) 6692861 in 2004 proposes a kind of high temperature (1000 ℃～2000 ℃) solid electrolyte DCFC, and its power density is about 10mW/cm
2This patent proposes a kind of fused carbonate electrolyte DCFC, 1000 ℃ of working temperatures.It is the weak point of this kind DCFC that working temperature height, power density are hanged down.Document [S.Zecevic, E.M.Patton, P.Parhami, Carbon2004,42,1983～1993.] use different cathode materials (mild steel, nickel, nickel foam, Fe2Ti etc.) the DCFC output performance to be tested gained maximum current density 270 mA/cm in
2, maximum power density 60 mW/cm
2, electrolyte is the molten caustic soda mixture, 630 ℃ of working temperatures.Document [N.J.Cherepy, P.Krueger, et al..Joumal of The Electrochemical Society.2005,152, A80～A87] in use different anode materials (coke, anthracite, active carbon etc.) that the battery voltage-current characteristic is tested, electrolyte is the fused carbonate mixture, 800 ℃ of working temperatures, and the gained maximum current density is about 150 mA/cm
2, maximum power density is 80 mW/cm
2
At present in the world relevant patent of DCFC and main research concentrate on improvements, optimize that electrolyte is formed, aspects such as improvement internal structure and development of new DCFC, test electrode material property, it is less to relate to the invention that how to improve direct carbon consuming cell power density and how to reduce working temperature.Current foreign latest DCFC can be under elevated operating temperature (800 ℃～1000 ℃) obtain higher power density, but power density and current density are lower during middle low temperature (500 ℃～650 ℃) operation.Low this problem of power density has hindered the practical application of DCFC, and therefore improving power density and current density becomes in the DCFC development and need one of problem that solves.In addition, direct carbon consuming cell at high temperature moves and has many problems inevitably: the cost of (1) fuel cell operation maintenance when hot operation is higher; (2) directly the carbon consuming cell electrolyte generally uses molten caustic soda or fused carbonate, and temperature rising inside battery and structural member are aggravated by electrolyte corrosion; (3) elevated operating temperature having relatively high expectations to electrode material.Therefore, reducing operating temperature is to need the problem that solves in the direct carbon consuming cell research field; Simultaneously, how obtaining higher power density when reducing the DCFC operating temperature becomes in the DCFC development and needs one of difficult point problem that solves.
Summary of the invention
A purpose of the present invention provides a kind of direct carbon consuming cell cathode material, the DCFC that uses this rare earth oxide composite cathode material is when middle temperature (600 ℃) is moved, can obtain higher power density and current density, when low temperature (500 ℃) moves, still can obtain higher power density and current density.
A purpose of the present invention provides a kind of preparation method of direct carbon consuming cell cathode material.
Direct carbon consuming cell cathode material of the present invention is a composite cathode material, and it comprises rare earth oxide, is made up of by the mole percentage composition following composition:
Ni 50～90％
Gd
2O
3 1～18％
CeO
2 1～20％
La
2O
3 0.5～7％
Nd
2O
3 1～7％
Yb
2O
3 0.5～7％
ZrO
2 1～4％
MgO 1～4％。
The preparation method of direct carbon consuming cell cathode material of the present invention, this method may further comprise the steps:
(1) takes by weighing the Gd of Ni, 1～1 8% that accounts for direct carbon consuming cell cathode material molar content 50～90%
2O
3, 1～20% CeO
2, 0.5～7% La
2O
3, 1～7% Nd
2O
3, 0.5～7% Yb
2O
3, 1～4% ZrO
2, 1～4% MgO, fully behind the mix grinding, take out oven dry with grinder (planetary ball mill); Gained negative electrode powder is placed mould, and thickness 1.5～6mm column type base substrate is made in unidirectional pressurization under 100～400MPa pressure;
(2) base substrate that step (1) is obtained places hot pressing furnace; under the nitrogen atmosphere protection, be warming up to 700 ℃～1250 ℃; heating rate is 5～10 ℃/min; pressure is 0.1～10MPa; constant temperature 0.5～10 hour is reduced to take out after the room temperature and is promptly obtained direct carbon consuming cell rare earth oxide composite cathode material of the present invention.
The DCFC that uses the direct carbon consuming cell cathode material of the present invention when 630 ℃ of work, maximum power density 102mW/cm
2, maximum current density 476mA/cm
2, improved power density and the current density of DCFC when middle temperature.The DCFC that uses direct carbon consuming cell cathode material of the present invention when 500 ℃ of work, maximum power density 72mW/cm
2, maximum current density 328mA/cm
2, use the DCFC of the direct carbon consuming cell cathode material of the present invention in the time of 500 ℃, to obtain higher output performance, promptly reduced the working temperature of DCFC.
DCFC rare earth oxide composite cathode material provided by the present invention also has following characteristics: this cathode material does not contain noble metal, and is cheap for manufacturing cost; The preparation technology that middle rare earth oxide composite cathode material of the present invention adopts is simple, is suitable for large-scale production, helps promoting the industrialization of direct carbon consuming cell.Use the fuel cell electric discharge performance of this cathode material stable, cathode material does not dissolve, and can not pollute fused electrolyte;
Description of drawings
Fig. 1. direct carbon consuming cell structural representation provided by the invention.
Fig. 2. the volt-ampere characteristic figure of the direct carbon consuming cell of rare earth oxide composite cathode material provided by the invention battery when working for 500 ℃ and 630 ℃.
Reference numeral
1. negative electrode 2. anodes 3. electrolyte 4. alumina crucibles
5. load 6. wireways 7. flowmeters
() 500 ℃ of power densities of 500 ℃ of voltage-to-current density curves (△)-current density curve
(■) 630 ℃ of power densities of 630 ℃ of voltage-to-current density curves (▲)-current density curve
Embodiment
Describe the present invention in detail below in conjunction with example and accompanying drawing.
The composition and the preparation technology of embodiment 1～10 rare earth oxide composite cathode material.
Each component molar content according to listed in the table 1 takes by weighing analytically pure Ni, Gd respectively
2O
3, Nd
2O
3, La
2O
3, Y
2O
3, CeO
2, MgO, ZrO
2, behind the abundant mix grinding of planetary ball mill, take out oven dry.Powder is placed diameter 30mm mould, and unidirectional pressurization is pressed into thickness 1.5～6mm column type base substrate under 100～400MPa pressure.Base substrate is placed hot pressing furnace, be warming up to 700 ℃～1250 ℃ under nitrogen atmosphere protection, pressure is 0.5～10MPa, and constant temperature 0.5～10 hour takes out after reducing to room temperature then, and it is stand-by to form the DCFC cathode material.
Table 1. cathode material component table (molar content)
Embodiment 11 makes up the DCFC element cell
Take by weighing analytically pure NaOH, LiOH, KOH, Al (OH) respectively
3, Y
2O
3, mix NaOH 20～30%, LiOH 10～20%, KOH 40～50%, Al (OH) by accounting for the electrolyte molar content
310～30%, Y
2O
31～15%, after fully mixing, take out oven dry as electrolyte.Anode and cathode spacing are 0.5～5cm, and the cathode air flow is 10～100ml/min.Anode material is a graphite, and negative electrode is respectively the material of embodiment 1～10.500 ℃～630 ℃ of working temperatures.Directly the carbon consuming cell unit cell structure as shown in Figure 1.
The test of embodiment 12 power densities
With the rare earth oxide composite cathode material of embodiment 3, place DCFC element cell test DCFC volt-ampere characteristic.Respectively at 500 ℃ of change curves of measuring DCFC power density and open circuit voltage with current density during with 630 ℃.Electrode effective area 3.23cm
2The voltage-current characteristic of battery as shown in Figure 2, as can be seen, the maximum power density 70mW/cm of DCFC in the time of 500 ℃
2, maximum current density is 328mA/cm
2The maximum power density of DCFC is 102mW/cm in the time of 630 ℃
2, maximum current density is 467mA/cm
2Table 2 is under 500 ℃ and 630 ℃, the experiment parameter of DCFC and battery performance.
Table 2.500 ℃ and 630 ℃ of DCFC parameters and performance
Claims (3)
1. direct carbon consuming cell cathode material, it is characterized in that: described direct carbon consuming cell cathode material is a composite cathode material, and it comprises rare earth oxide, is made up of by a mole percentage composition following composition:
Ni 50～90％
Gd
2O
3 1～18％
CeO
2 1～20％
La
2O
3 0.5～7％
Nd
2O
3 1～7％
Yb
2O
3 0.5～7％
ZrO
2 1～4％
MgO 1～4％。
2. the preparation method of a direct carbon consuming cell cathode material according to claim 1, it is characterized in that: this method may further comprise the steps:
(1) takes by weighing the Ni that accounts for direct carbon consuming cell cathode material molar content 50～90%, 1～18% Gd
2O
3, 1～20% CeO
2, 0.5～7% La
2O
3, 1～7% Nd
2O
3, 0.5～7% Yb
2O
3, 1～4% ZrO
2, 1～4% MgO, behind the abundant mix grinding of grinder, take out oven dry; Gained negative electrode powder is placed mould, and thickness 1.5～6mm base substrate is made in unidirectional pressurization under 100～400MPa pressure;
(2) base substrate that step (1) is obtained places hot pressing furnace; be warming up to 700 ℃～1250 ℃ under inert gas shielding, heating rate is 5～10 ℃/min, and pressure is 0.1～10MPa; constant temperature is reduced to take out after the room temperature and is promptly obtained direct carbon consuming cell rare earth oxide composite cathode material.
3. method according to claim 2 is characterized in that: described constant temperature time is 0.5～10 hour.
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|---|---|---|---|
| CNB2005101177391A CN100392894C (en) | 2005-11-09 | 2005-11-09 | A cathode material for direct carbon fuel cell and its manufacture method |
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|---|---|---|---|
| CNB2005101177391A CN100392894C (en) | 2005-11-09 | 2005-11-09 | A cathode material for direct carbon fuel cell and its manufacture method |
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|---|---|
| CN1964112A CN1964112A (en) | 2007-05-16 |
| CN100392894C true CN100392894C (en) | 2008-06-04 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105206846B (en) * | 2015-09-14 | 2016-10-12 | 山西宇翔信息技术有限公司 | A kind of nickel lanthanide composite material negative electrode and Direct Carbon Fuel Cells thereof and preparation method |
| CN105206858B (en) * | 2015-09-14 | 2016-10-26 | 山西宇翔信息技术有限公司 | A kind of fluid-bed electrode carbon fuel cell device and control method thereof |
| CN105186024B (en) * | 2015-09-18 | 2017-03-22 | 山西宇翔信息技术有限公司 | Direct carbon fuel cell using eutectic fusible hydroxide mixture as electrolyte |
| CN105206859B (en) * | 2015-09-29 | 2016-08-17 | 北京理工大学 | The micron carbon fluid gas-phase of Direct Carbon Fuel Cells is made bulb apparatus and makes bubble method |
| CN110429311B (en) * | 2019-07-16 | 2020-12-08 | 华中科技大学 | Anode chamber, method and battery for greatly improving MC-DCFC power density |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3970474A (en) * | 1975-08-11 | 1976-07-20 | Stanford Research Institute | Method and apparatus for electrochemical generation of power from carbonaceous fuels |
| US6692861B2 (en) * | 1998-03-03 | 2004-02-17 | Celltech Power, Inc. | Carbon-oxygen fuel cell |
-
2005
- 2005-11-09 CN CNB2005101177391A patent/CN100392894C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3970474A (en) * | 1975-08-11 | 1976-07-20 | Stanford Research Institute | Method and apparatus for electrochemical generation of power from carbonaceous fuels |
| US6692861B2 (en) * | 1998-03-03 | 2004-02-17 | Celltech Power, Inc. | Carbon-oxygen fuel cell |
Non-Patent Citations (1)
| Title |
|---|
| Carbon-air fuel cell without a reforming process. Strahinja Zecevic, Edward M. Patton, Parviz Parhami.Carbon,Vol.42 . 2004 * |
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