CN102306806A - Ternary composite matrix anode material for molten carbonate fuel cell (MCFC) and preparation method of ternary composite matrix anode material - Google Patents
Ternary composite matrix anode material for molten carbonate fuel cell (MCFC) and preparation method of ternary composite matrix anode material Download PDFInfo
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- CN102306806A CN102306806A CN201110243588A CN201110243588A CN102306806A CN 102306806 A CN102306806 A CN 102306806A CN 201110243588 A CN201110243588 A CN 201110243588A CN 201110243588 A CN201110243588 A CN 201110243588A CN 102306806 A CN102306806 A CN 102306806A
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Abstract
The invention discloses a ternary composite matrix anode material for a molten carbonate fuel cell (MCFC) and a preparation method of the ternary composite matrix anode material. The preparation method comprises the following steps of: depositing two nano ceramic particles with high properties on a porous nickel matrix simultaneously; and sintering under an inert atmosphere, and thus obtaining a composite matrix anode, wherein the nano ceramic particles mainly comprise LiCoO2 and one of LiFeO2 and CeO2, and the deposited polynary nano ceramic particle layer is uniformly distributed on the surface of the porous nickel matrix and has high bonding force together with the matrix. The ternary composite matrix anode material has high mechanical strength, high deformation resistance, high dissolving resistance, a simple preparation process and extremely short preparation time and can be used for MCFC stack actual industries.
Description
Technical field
The invention belongs to the new energy materials technical field, be specifically related to a kind of molten carbonate fuel cell ternary complex matrix cathode material and preparation method thereof.
Background technology
Molten carbonate fuel cell (MCFC) is because of it has efficiently, cleaning, fuel source extensively and not need use noble metal to make advantages such as catalyst, becomes one of the Blast Furnace Top Gas Recovery Turbine Unit (TRT) that chemical energy is converted into the tool application prospect of electric energy.And realized commercially producing.The slow dissolving of right its negative electrode and the battery short circuit problem that causes thereof are to influence battery life and the principal element that hinders its further large-scale commercial always.Ideal cathode material should possess good toughness and mechanical strength, good anti-deformation, antilysis and chemical property.At present, do not find to substitute fully the one-component material of traditional lithiated nickel oxide negative electrode as yet, therefore, composite cathode material becomes the research focus because of the premium properties that has each material concurrently.Present most of multi-element composite material all is to form with mixed sinterings such as ceramic powders, need fully mixing uneven to prevent material component in the making, and made composite cathode has certain fragility.And the electrode material area that uses in the actual MCFC industry is big and thin thickness, thereby this just requires material to have excellent mechanical intensity and toughness helps the battery pile installation, to avoid influencing battery life because of the results in premature failure of material.In addition, preparation time also is one of important indicator that realizes suitability for industrialized production.
Summary of the invention
The objective of the invention is to prepare at short notice have good mechanical strength, good anti-deformation and the polynary composite cathode material of antilysis performance, can be applicable to actual MCFC battery pile commercial production.
Be to realize above-mentioned purpose, the technical scheme that the present invention taked is: prepare the nano-ceramic particle of several function admirables, two kinds of nanoparticulate dispersed are wherein processed suspension in the dispersant that is fit to.With the nickel porous material is negative electrode; Platinum electrode is an anode; Adopt electrophoretic deposition technique; Control parameters such as suitable suspension concentration, pH of suspension value, electrophoretic voltage and electrophoresis time; With nano-particle modified in the porous Ni-base surface; And in inert atmosphere, handled 1 hour, process ternary complex matrix cathode material.
Molten carbonate fuel cell ternary complex matrix cathode material among the present invention is porous (nano-LiCoO
2-CeO
2)-Ni or porous (nano-LiCoO
2-LiFeO
2)-Ni material, its porosity are 65%～75%; Wherein to account for the mass percent of complex matrix cathode material be 1.2～2.2% to nano-ceramic particle coating; Described nano-ceramic particle coating is nano-LiCoO
2-CeO
2Or nano-LiCoO
2-LiFeO
2
The preparation method of above-mentioned material may further comprise the steps:
Step 1. adopts the gel combustion method, and 600 ℃～700 ℃ of control calcining heats are prepared LiCoO
2, CeO
2And LiFeO
2Nano particle;
Step 2. is scattered in the nano particle group processes suspension in the dispersant;
Described nano particle group is LiCoO
2/ CeO
2Or LiCoO
2/ LiFeO
2When the nano particle group is LiCoO
2/ CeO
2The time, LiCoO
2With CeO
2Mol ratio be 3～6:1, its corresponding dispersant is isopropyl alcohol and ethylene glycol mixture, the volume ratio of isopropyl alcohol and ethylene glycol is 2～5:1; When the nano particle group is LiCoO
2/ LiFeO
2The time, LiCoO
2With LiFeO
2Mol ratio be 4～8:1, its corresponding dispersant is an isopropyl alcohol;
Described nano particle group and suspension ratio are: 0.1g～0.5g/50ml;
Step 3. is regulated pH value to 2～6 of suspension;
Step 4. is in the suspension that step 3 is processed; With the nickel porous is negative electrode, and platinized platinum is an anode, and electrode distance is 2 centimetres～3.5 centimetres; The control electrophoretic voltage is that 35 volts～100 volts, electrophoresis time are 1 minute～5 minutes, and the nano particle group is modified to the porous nickel surface;
The sample that step 5 makes step 4 in 600 ℃～700 ℃ sintering 1 hour, is processed ternary complex matrix cathode material in inert atmosphere.
In the said method, the electrode distance in the step 4 is preferably 2.5 centimetres, and electrophoretic voltage is preferably 55 volts～75 volts, electrophoresis time and is preferably 1.5 minutes～and 2.5 minutes.
Compared with prior art, the invention has the beneficial effects as follows:
Ternary complex matrix negative electrode has good toughness and intensity, is convenient to the MCFC battery pile and installs, and the startup stage of MCFC, can converted in-situ be the compound work negative electrode of ternary of function admirable.Compare with traditional porous Ni-base negative electrode, ternary complex matrix negative electrode demonstrates good anti-deformation and antilysis performance in simulation is MCFC the startup stage.The nano particle coating on composite cathode material surface is evenly fine and close, and is good with porous Ni-base material bond strength.Thickness of coating is very thin, can the original loose structure of fine maintenance.Preparation technology is simple for ternary complex matrix cathode material, and feed liquid can be recycled, easy to operate and repetition.Manufacturing cycle is extremely short, is easy to realize large-scale industrial production.
The preparation method of complex matrix negative electrode of the present invention is simple, and controlled and repeated high, manufacturing cycle is short.Utilize the good toughness of metal and nano-ceramic particle, be applicable to the MCFC actual industrial.
Description of drawings
Fig. 1 is the LiCoO of preparation
2-CeO
2The sem photograph of-Ni ternary complex matrix cathode material.
Fig. 2 is the LiCoO of preparation
2-CeO
2The energy dispersive spectrogram of-Ni ternary complex matrix cathode material.
Fig. 3 is the LiCoO of preparation
2-CeO
2The inflection curves of-Ni ternary complex matrix cathode material under simulation MCFC startup and service conditions.
Fig. 4 is LiCoO
2-CeO
2-Ni substrate cathode material is the sem photograph behind deformation/dissolution experiment in position.
Fig. 5 is LiCoO
2-CeO
2-Ni substrate cathode material is the Ni distribution diagram of element behind deformation/dissolution experiment in position.
Fig. 6 is LiCoO
2-CeO
2-Ni substrate cathode material is the Co distribution diagram of element behind deformation/dissolution experiment in position.
Fig. 7 is LiCoO
2-CeO
2-Ni substrate cathode material is the Ce distribution diagram of element behind deformation/dissolution experiment in position.
Fig. 8 is the LiCoO of preparation
2-LiFeO
2The sem photograph of-Ni ternary complex matrix cathode material.
Fig. 9 is the LiCoO of preparation
2-LiFeO
2The energy dispersive spectrogram of-Ni ternary complex matrix cathode material.
Figure 10 is the LiCoO of preparation
2-LiFeO
2The inflection curves of-Ni ternary complex matrix cathode material under simulation MCFC startup and service conditions.
Figure 11 is LiCoO
2-LiFeO
2-Ni substrate cathode material is the sem photograph behind deformation/dissolution experiment in position.
Figure 12 is LiCoO
2-LiFeO
2-Ni substrate cathode material is the Ni distribution diagram of element behind deformation/dissolution experiment in position.
Figure 13 is LiCoO
2-LiFeO
2-Ni substrate cathode material is the Co distribution diagram of element behind deformation/dissolution experiment in position.
Figure 14 is LiCoO
2-LiFeO
2-Ni substrate cathode material is the Fe distribution diagram of element behind deformation/dissolution experiment in position.
Embodiment
Below in conjunction with embodiment the present invention is done further explanation, but the scope that the present invention requires to protect is not limited to the scope that embodiment expresses.
Embodiment 1
Ternary complex matrix negative electrode in the present embodiment obtains through following steps:
Adopt the gel combustion method, control 650 ℃ calcining heat, prepare LiCoO
2And CeO
2Two kinds of nano particles.With mol ratio is the 0.2g LiCoO of 4:1
2/ CeO
2Mixture of nanoparticles is scattered in the isopropyl alcohol and ethylene glycol mixtures that the 50ml volume ratio is 3:1, processes suspension, regulates pH value to 2.5～3 of suspension.In the suspension of processing, be negative electrode with the nickel porous, platinized platinum is an anode, and electrode distance is 2.5 centimetres, and the control electrophoretic voltage is that 65 volts, electrophoresis time are 2 minutes, and the nano particle group is modified to the porous nickel surface.In inert atmosphere,, process porous (nano-LiCoO in 650 ℃ of sintering 1 hour
2-CeO
2)-Ni ternary complex matrix cathode material.
The surface topography of the complex matrix negative electrode of preparation is measured through scanning electron microscopy, as shown in Figure 1.The nano-ceramic particle of deposition is evenly distributed on the porous Ni-base surface, forms fine and close coating coating.Even in the hole, coating is still evenly fine and close.Thickness of coating is thin, and the complex matrix negative electrode is kept original loose structure well.
The element of complex matrix cathode material is formed through X ray energy dispersive spectrum mensuration, as shown in Figure 2.Except that nickel element, also there are cobalt, cerium and oxygen element in the material.This result shows, LiCoO
2And CeO
2Two kinds of nano particles have been modified to porous Ni substrate surface simultaneously.
Deformation/the solubility property of complex matrix cathode material is through self-built original position deformation test macro and Atomic Absorption Spectrometry.The complex matrix cathode material is (CO in negative electrode atmosphere
2: O
2: N
2Be 0.20:0.15:0.65) in 650 ℃ and 3.51 * 10
5Nm
-2Inflection curves under bearing a heavy burden as shown in Figure 3.Fig. 3 shows, traditional porous Ni-base negative electrode simulation MCFC start and service conditions under, deformation is obvious, especially start preceding 20 hours, gradate with nickel porous and to be lithiated nickel oxide work negative electrode, deformation slows down.Compare with traditional porous Ni-base negative electrode, obvious deformation does not take place in ternary complex matrix negative electrode.Melt in the salt nickel ion concentration after the experiment and measure the result and show, in the deformation process, the nickel stripping is serious (2.8936mg/L) in position for the nickel porous material; And trielement composite material only has the nickel stripping (0.5178 mg/L) of trace.The result shows, compares with traditional porous Ni-base negative electrode, and the ternary complex matrix negative electrode of preparation has good anti-deformation/antilysis performance.
The surface topography of complex matrix negative electrode behind deformation/dissolution experiment measured through scanning electron microscopy, as shown in Figure 4.Compare with traditional nickel porous material, composite material in position behind deformation/dissolution experiment its surface topography obvious change does not take place, the surface is still closely coating nano-ceramic particle.Particle size increases to some extent, mainly is owing to be converted in the process of work negative electrode LiCoO at basis material
2Ceramic particle and matrix nickel have formed LiCo
yNi
1-yThe O cenotype.
The element of complex matrix negative electrode behind deformation/dissolution experiment distributes and measures through X ray energy dispersive spectrum, like Fig. 5, Fig. 6 and shown in Figure 7.It is relevant with the loose structure of material that element distributes, and the hole inner region is darker, is owing to ray produce power loss when internal reflection goes out in the hole.Cobalt and Ce elements in the material distribute very evenly, and with matrix in nickel element distribute consistent.The result shows that after the deformation experiment, the nano ceramics coating of composite material still coats densification at matrix surface, deformation and dissolving that therefore very big degree has been slowed down material.
Embodiment 2
Ternary complex matrix negative electrode in the present embodiment obtains through following steps:
Adopt the gel combustion method, control 650 ℃ calcining heat, prepare LiCoO
2And CeO
2Two kinds of nano particles.With mol ratio is the 0.2g LiCoO of 3:1
2/ CeO
2Mixture of nanoparticles is scattered in the isopropyl alcohol and ethylene glycol mixtures that the 50ml volume ratio is 2:1, processes suspension, regulates pH value to 2.5～3 of suspension.In the suspension of processing, be negative electrode with the nickel porous, platinized platinum is an anode, and electrode distance is 2.5 centimetres, and the control electrophoretic voltage is that 55 volts, electrophoresis time are 2 minutes, and the nano particle group is modified to the porous nickel surface.In inert atmosphere,, process porous (nano-LiCoO in 650 ℃ of sintering 1 hour
2-CeO
2)-Ni ternary complex matrix cathode material.
Prepared material is similar among surface topography and the element composition of the ternary complex matrix cathode material of preparation and the embodiment 1.The nano-ceramic particle coating even compact of deposition; Element in the material comprises nickel element, cobalt element, Ce elements and oxygen element, i.e. LiCoO
2And CeO
2Two kinds of nano particles have been modified to porous Ni substrate surface simultaneously.
Equally, the complex matrix negative electrode does not have obvious deformation to take place in deformation experiment, melts after the experiment that nickel ion concentration is determined as 0.6257mg/L in the salt.After element distribution image after the experiment showed the deformation experiment, the nano ceramics coating of composite material still coated densification at matrix surface, has largely slowed down the deformation and the dissolving of material.
Embodiment 3
Ternary complex matrix negative electrode in the present embodiment obtains through following steps:
Adopt the gel combustion method, control 650 ℃ calcining heat, prepare LiCoO
2And CeO
2Two kinds of nano particles.With mol ratio is the 0.2g LiCoO of 6:1
2/ CeO
2Mixture of nanoparticles is scattered in the isopropyl alcohol and ethylene glycol mixtures that the 50ml volume ratio is 5:1, processes suspension, regulates pH value to 2.5～3 of suspension.In the suspension of processing, be negative electrode with the nickel porous, platinized platinum is an anode, and electrode distance is 2.5 centimetres, and the control electrophoretic voltage is that 75 volts, electrophoresis time are 2 minutes, and the nano particle group is modified to the porous nickel surface.In inert atmosphere,, process porous (nano-LiCoO in 650 ℃ of sintering 1 hour
2-CeO
2)-Ni ternary complex matrix cathode material.
Prepared material is similar among surface topography and the element composition of the ternary complex matrix cathode material of preparation and the embodiment 1.The nano-ceramic particle coating even compact of deposition; Element in the material comprises nickel element, cobalt element, Ce elements and oxygen element, i.e. LiCoO
2And CeO
2Two kinds of nano particles have been modified to porous Ni substrate surface simultaneously.
Equally, the complex matrix negative electrode does not have obvious deformation to take place in deformation experiment, melts after the experiment that nickel ion concentration is determined as 0.3016mg/L in the salt.After element distribution image after the experiment showed the deformation experiment, the nano ceramics coating of composite material still coated densification at matrix surface, deformation and dissolving that very big degree has been slowed down material.
Embodiment 4
Ternary complex matrix negative electrode in the present embodiment obtains through following steps:
Adopt the gel combustion method, control 650 ℃ calcining heat, prepare LiCoO
2And LiFeO
2Two kinds of nano particles.With mol ratio is the 0.2g LiCoO of 6:1
2/ LiFeO
2Mixture of nanoparticles is scattered in the isopropyl alcohol of 50ml, processes suspension, regulates pH value to 2.5～3 of suspension.In the suspension of processing, be negative electrode with the nickel porous, platinized platinum is an anode, and electrode distance is 2.5 centimetres, and the control electrophoretic voltage is that 65 volts, electrophoresis time are 2 minutes, and the nano particle group is modified to the porous nickel surface.In inert atmosphere,, process porous (nano-LiCoO in 650 ℃ of sintering 1 hour
2-LiFeO
2)-Ni ternary complex matrix cathode material.
The surface topography of the complex matrix negative electrode of preparation is measured through scanning electron microscopy, as shown in Figure 8.The nano-ceramic particle of deposition is evenly distributed on the porous Ni-base surface, forms fine and close coating layer.Even in the hole, coating is still evenly fine and close.Thickness of coating is thin, and the complex matrix negative electrode is kept original loose structure well.
The element of complex matrix cathode material is formed through X ray energy dispersive spectrum mensuration, as shown in Figure 9.Except that nickel element, also there are cobalt, iron and oxygen element in the material.This result shows, LiCoO
2And LiFeO
2Two kinds of nano particles have been modified to porous Ni substrate surface simultaneously.
Deformation/the solubility property of complex matrix cathode material is through self-built original position deformation test macro and Atomic Absorption Spectrometry.The complex matrix cathode material is (CO in negative electrode atmosphere
2: O
2: N
2Be 0.20:0.15:0.65) in 650 ℃ and 3.51 * 10
5Nm
-2Inflection curves under bearing a heavy burden as shown in figure 10.Figure 10 shows, traditional porous Ni-base negative electrode simulation MCFC start and service conditions under, deformation is obvious, especially start preceding 20 hours, gradate with nickel porous and to be lithiated nickel oxide work negative electrode, deformation slows down.Compare with traditional porous Ni-base negative electrode, obvious deformation does not take place in ternary complex matrix negative electrode.Melt in the salt nickel ion concentration after the experiment and measure the result and show, in the deformation process, the nickel stripping is serious (2.8936mg/L) in position for the nickel porous material; And trielement composite material only has the nickel stripping (0.1783mg/L) of denier.The result shows, compares with traditional porous Ni-base negative electrode, and the ternary complex matrix negative electrode of preparation has good anti-deformation/antilysis performance, and compares with 3 with embodiment 1,2, and it is lower to melt in the salt nickel ion concentration, is because LiFeO
2The solubility of component in melting salt is extremely low.
The surface topography of complex matrix negative electrode behind deformation/dissolution experiment measured through scanning electron microscopy, as shown in figure 11.Compare with traditional nickel porous material, composite material in position behind deformation/dissolution experiment its surface topography obvious change does not take place, the surface is still closely coating nano-ceramic particle.Particle size increases to some extent, mainly is owing to be converted in the process of work negative electrode LiCoO at basis material
2Ceramic particle and matrix nickel have formed LiCo
yNi
1-yThe O cenotype.
The element of complex matrix negative electrode behind deformation/dissolution experiment distributes and measures through X ray energy dispersive spectrum, like Figure 12, Figure 13 and shown in Figure 14.It is relevant with the loose structure of material that element distributes, and the hole inner region is darker, is owing to ray produce power loss when internal reflection goes out in the hole.Cobalt and ferro element in the material distribute very evenly, and with matrix in nickel element distribute consistent.The result shows that after the deformation experiment, the nano ceramics coating of composite material still coats densification at matrix surface, deformation and dissolving that very big degree has been slowed down material.
Embodiment 5
Ternary complex matrix negative electrode in the present embodiment obtains through following steps:
Adopt the gel combustion method, control 650 ℃ calcining heat, prepare LiCoO
2And LiFeO
2Two kinds of nano particles.With mol ratio is the 0.2g LiCoO of 4:1
2/ LiFeO
2Mixture of nanoparticles is scattered in the isopropyl alcohol of 50ml, processes suspension, regulates pH value to 2.5～3 of suspension.In the suspension of processing, be negative electrode with the nickel porous, platinized platinum is an anode, and electrode distance is 2.5 centimetres, and the control electrophoretic voltage is that 55 volts, electrophoresis time are 2 minutes, and the nano particle group is modified to the porous nickel surface.In inert atmosphere,, process porous (nano-LiCoO in 650 ℃ of sintering 1 hour
2-LiFeO
2)-Ni ternary complex matrix cathode material.
Prepared material is similar among surface topography and the element composition of the ternary complex matrix cathode material of preparation and the embodiment 4.The nano-ceramic particle coating even compact of deposition; Element in the material comprises nickel element, cobalt element, ferro element and oxygen element, i.e. LiCoO
2And LiFeO
2Two kinds of nano particles have been modified to porous Ni substrate surface simultaneously.
Equally, the complex matrix negative electrode does not have obvious deformation to take place in deformation experiment, melts after the experiment that nickel ion concentration is determined as 0.1088mg/L in the salt.After element distribution image after the experiment showed the deformation experiment, the nano ceramics coating of composite material still coated densification at matrix surface, deformation and dissolving that therefore very big degree has been slowed down material.
Embodiment 6
Ternary complex matrix negative electrode in the present embodiment obtains through following steps:
Adopt the gel combustion method, control 650 ℃ calcining heat, prepare LiCoO
2And LiFeO
2Two kinds of nano particles.With mol ratio is the 0.2g LiCoO of 8:1
2/ LiFeO
2Mixture of nanoparticles is scattered in the isopropyl alcohol of 50ml, processes suspension, regulates pH value to 2.5～3 of suspension.In the suspension of processing, be negative electrode with the nickel porous, platinized platinum is an anode, and electrode distance is 2.5 centimetres, and the control electrophoretic voltage is that 75 volts, electrophoresis time are 2 minutes, and the nano particle group is modified to the porous nickel surface.In inert atmosphere,, process porous (nano-LiCoO in 650 ℃ of sintering 1 hour
2-LiFeO
2)-Ni ternary complex matrix cathode material.
Prepared material is similar among surface topography and the element composition of the ternary complex matrix cathode material of preparation and the embodiment 4.The nano-ceramic particle coating even compact of deposition; Element in the material comprises nickel element, cobalt element, ferro element and oxygen element, i.e. LiCoO
2And LiFeO
2Two kinds of nano particles have been modified to porous Ni substrate surface simultaneously.
Equally, the complex matrix negative electrode does not have obvious deformation to take place in deformation experiment, melts after the experiment that nickel ion concentration is determined as 0.2376mg/L in the salt.After element distribution image after the experiment showed the deformation experiment, the nano ceramics coating of composite material still coated densification at matrix surface, has largely slowed down the deformation and the dissolving of material.
Claims (3)
1. molten carbonate fuel cell ternary complex matrix cathode material is characterized in that:
This material is porous (nano-LiCoO
2-CeO
2)-Ni or porous (nano-LiCoO
2-LiFeO
2)-Ni material, its porosity are 65%～75%; Wherein to account for the mass percent of complex matrix cathode material be 1.2～2.2% to nano-ceramic particle coating; Described nano-ceramic particle coating is nano-LiCoO
2-CeO
2Or nano-LiCoO
2-LiFeO
2
2. molten carbonate fuel cell ternary complex matrix cathode material preparation method is characterized in that this method may further comprise the steps:
Step 2-1. adopts the gel combustion method, and 600 ℃～700 ℃ of control calcining heats are prepared LiCoO
2, CeO
2And LiFeO
2Nano particle;
Step 2-2. is scattered in the nano particle group and processes suspension in the dispersant;
Described nano particle group is LiCoO
2/ CeO
2Or LiCoO
2/ LiFeO
2When the nano particle group is LiCoO
2/ CeO
2The time, LiCoO
2With CeO
2Mol ratio be 3～6:1, its corresponding dispersant is isopropyl alcohol and ethylene glycol mixture, the volume ratio of isopropyl alcohol and ethylene glycol is 2～5:1; When the nano particle group is LiCoO
2/ LiFeO
2The time, LiCoO
2With LiFeO
2Mol ratio be 4～8:1, its corresponding dispersant is an isopropyl alcohol;
Described nano particle group and suspension ratio are: 0.1g～0.5g/50ml;
Step 2-3. regulates pH value to 2～6 of suspension;
Step 2-4. is in the suspension that step 2-3 processes; With the nickel porous is negative electrode, and platinized platinum is an anode, and electrode distance is 2 centimetres～3.5 centimetres; The control electrophoretic voltage is that 35 volts～100 volts, electrophoresis time are 1 minute～5 minutes, and the nano particle group is modified to the porous nickel surface;
The sample that step 2-5 makes step 2-4 in 600 ℃～700 ℃ sintering 1 hour, is processed ternary complex matrix cathode material in inert atmosphere.
3. preparation method according to claim 2 is characterized in that the electrode distance among this method step 2-4 is 2.5 centimetres, and electrophoretic voltage is that 55 volts～75 volts, electrophoresis time are 1.5 minutes～2.5 minutes.
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