CN109713346A - Adulterate apatite-type lanthanum silicate and its preparation method and application in silicon position - Google Patents
Adulterate apatite-type lanthanum silicate and its preparation method and application in silicon position Download PDFInfo
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Abstract
The present invention relates to field of inorganic materials, a kind of silicon position doping apatite-type lanthanum silicate and its preparation method and application, the general structure of the silicon position doping apatite-type lanthanum silicate are as follows: La are disclosed9.33+ xSi6‑yMyO26+δWherein, 0≤x≤0.67,0 < y≤2,0≤δ≤1, preparation method includes: under the conditions of precipitation reaction, according to stoichiometric ratio by soluble lanthanum salt, the soluble-salt and soluble silicate of metallic element M, contacted in water with precipitating reagent, isolated solid sediment, and the solid sediment is optionally dried, and roasting；Wherein, metallic element M is selected from least one of the IIth A race metal of the periodic table of elements, group IIIA metal, the IVth A race metal, the Ith B race metal, II B-group metal, the Vth B race metal, group VIB metal, the VIIth B race metal and group VIII metal.Have the characteristics that phase is pure, at low cost using the silicon position doping apatite-type lanthanum silicate of method provided by the invention preparation.
Description
Technical field
The present invention relates to a kind of silicon position doping apatite-type lanthanum silicates and its preparation method and application.
Background technique
Fuel cell has energy conversion rate high, environmental-friendly, strong and safe and reliable without mechanicalness noise, different capacity adaptation
The advantages that, the problems such as gradually replacing conventional power generation systems, and alleviate environmental pollution, solve electricity shortage.It has now been developed
Pluralities of fuel battery is one such if solid oxide fuel cell (SOFC).Solid oxide fuel cell conduct
A kind of system converting electric energy for chemical energy, has many advantages, such as energy conversion efficiency and low pollution, is most potential at present
One of new energy.Electrolyte is the core component of solid oxide fuel cell, its main function is transmitting oxonium ion,
Completely cut off fuel and oxygen simultaneously.The electrolyte of solid oxide fuel cell mainly includes fluorite type electrolyte, Ca-Ti ore type electricity
Solve matter and apatite-type electrolyte.Wherein, apatite-type electrolyte is the ionic conductivity with higher and low under middle low temperature
The novel solid electrolyte of activation energy.The activation energy of apatite-type lanthanum silicate is low, hot expansibility is moderate, is middle low-temperature solid oxygen
A kind of candidate material of compound fuel-cell electrolyte；But the oxygen ionic conductivity of apatite-type lanthanum silicate electrolyte is relatively low,
Doped ions are needed to improve its conductivity, and the method often having on document includes that the doping of lanthanum position and silicon position adulterate two kinds.
The method reported in the literature for being usually used in silicon position doped chemical is solid-state fusion method and sol-gel method.For example, literary
Solid State Ionics is offered, 2011 (185) 18-26 propose the method for a kind of doping of silicon position Mg, Ge or Al, using
Solid-state fusion method；Document Materials Research Bulletin, 2012 (47) 719-723 propose a kind of silicon position doping
The method of Co, using sol-gel method.By analysis document discovery, although the cost of material that solid-state fusion method uses is just
Preferably, but the apatite-type electrolyte phase of preparation is impure, Chang Hanyou lanthana impurity；Although and sol-gel method can be prepared
The apatite-type electrolyte of pure phase state, but the higher tetraethyl orthosilicate of price is used, increase production cost.
Summary of the invention
The purpose of the invention is to overcome defect problem of the existing technology, a kind of new silicon position doping phosphorus ash is provided
The preparation method of stone-type lanthanum silicate and silicon position obtained by this method doping apatite-type lanthanum silicate and its application, using the present invention
Method pure phase state silicon position doping apatite-type electrolyte can be made, and method is simple, mild condition, low in cost.
To achieve the goals above, one aspect of the present invention provides a kind of preparation side of silicon position doping apatite-type lanthanum silicate
Method, wherein the general structure of the silicon position doping apatite-type lanthanum silicate are as follows: La9.33+xSi6-yMyO26+δ, wherein 0≤x≤
0.67,0 < y≤2,0≤δ≤1, the preparation method include: under the conditions of precipitation reaction, will be soluble according to stoichiometric ratio
The soluble-salt and soluble silicate of lanthanum salt, metallic element M are contacted with precipitating reagent, in water so that soluble silicate
Metal cation is precipitated respectively with precipitating reagent, isolated solid sediment, and solid sediment progress is optional
Drying, and roasting；
Wherein, metallic element M is selected from the IIth A race metal of the periodic table of elements, group IIIA metal, the IVth A race metal, the Ith B
In race's metal, II B-group metal, the Vth B race metal, group VIB metal, the VIIth B race metal and group VIII metal at least
It is a kind of.
Second aspect of the present invention provides a kind of silicon position doping apatite-type lanthanum silicate of preparation of the method according to the present invention,
Wherein, the general structure of the silicon position doping apatite-type lanthanum silicate are as follows: La9.33+xSi6-yMyO26+δ, wherein 0≤x≤0.67,0
< y≤2,0≤δ≤1, M be selected from the IIth A race metal of the periodic table of elements, group IIIA metal, the IVth A race metal, the Ith B race metal,
At least one of II B-group metal, the Vth B race metal, group VIB metal, the VIIth B race metal and group VIII metal.
It is solid in preparation that the third aspect of the present invention provides a kind of silicon position doping apatite-type lanthanum silicate provided by the present invention
Application in oxide body fuel-cell electrolyte.
Method provided by the invention, instead of tetraethyl orthosilicate, prepares the doping of silicon position using the precipitation method with cheap silicate
Apatite-type lanthanum silicate, preparation method is simple, and maturing temperature is low, and the silicon position doping apatite-type lanthanum silicate prepared has phase
Feature pure, at low cost.
Detailed description of the invention
Fig. 1 is the XRD diagram of doping apatite-type lanthanum silicate in silicon position prepared by the embodiment of the present invention 1；
Fig. 2 is the XRD diagram of doping apatite-type lanthanum silicate in silicon position prepared by the embodiment of the present invention 2；
Fig. 3 is the XRD diagram of doping apatite-type lanthanum silicate in silicon position prepared by the embodiment of the present invention 3.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The preparation method of the silicon position doping apatite-type lanthanum silicate provided according to the present invention, wherein adulterate phosphorus in the silicon position
The general structure of grey stone-type lanthanum silicate are as follows: La9.33+xSi6-yMyO26+δ, wherein 0≤x≤0.67,0 < y≤2,0≤δ≤1 are described
Preparation method includes: under the conditions of precipitation reaction, according to stoichiometric ratio by soluble lanthanum salt, the soluble-salt of metallic element M
And soluble silicate, it is contacted in water with precipitating reagent, so that soluble silicate and precipitating reagent are respectively by soluble-salt
Precipitated cationic, isolated solid sediment, and the solid sediment is optionally dried, and roasting；
Wherein, metallic element M is selected from the IIth A race metal of the periodic table of elements, group IIIA metal, the IVth A race metal, the Ith B
In race's metal, II B-group metal, the Vth B race metal, group VIB metal, the VIIth B race metal and group VIII metal at least
It is a kind of.
In the present invention, used silicate is soluble easily in water, and how to make silicate ion whole Precipitation is reaction
Key.Present invention employs the precipitation method to precipitate silicate ion completely.In reaction of the present invention, using lanthanum ion and
The characteristic that metallic element M ion is reacted with silicate ion makes silicate ion Precipitation in the form of silicate, extra
The aqueous solution of the aqueous solution or precipitating reagent of lanthanum ion and metal M ion and precipitating reagent alkaline matter weak (in strong) sour weak base salt is anti-
Hydroxide precipitating or lanthanum salt precipitating, M salt precipitating should be generated, silicate, hydroxide precipitating/lanthanum salt precipitating, M salt are deposited in one
Determine roasting temperature and generates silicon position doping apatite-type lanthanum silicate.
According to the present invention, soluble lanthanum salt, the use of the soluble-salt of metallic element M and soluble silicate and precipitating reagent
Amount can be weighed according to stoichiometric ratio so that meet silicon position doping apatite-type lanthanum silicate general structure in La,
The atomic ratio of Si, M, O.
According to the present invention, metallic element M is preferably selected from Mg, Al, Ga, In, Sn, Ge, Cu, Zn, Nb, W, Mn, Fe, Co, Ni
One of or it is a variety of, be more preferably selected from one of Al, Cu and Fe or a variety of.
In the present invention, the cation of the soluble-salt includes lanthanum ion and metallic element M in soluble lanthanum salt
The M ion of soluble-salt, for example, if the soluble-salt of metallic element M is zinc nitrate, what the cation of the soluble-salt referred to
It is zinc ion (generally Zn2+).In this regard, those skilled in the art can know that this is no longer going to repeat them.
According to the present invention, as long as guaranteeing to claim according to the stoichiometric ratio in silicon position doping apatite-type lanthanum silicate general structure
Take stoichiometric ratio by soluble lanthanum salt, the soluble-salt and soluble silicate of metallic element M, and in water with precipitating reagent
Contact, so that soluble silicate and precipitating reagent be respectively by the precipitated cationic of soluble-salt, and by isolated solid sediment
It carries out optionally dry and roasts the purpose of the present invention can be realized, in the present invention, the solubility lanthanum salt, metallic element M
Optional wider range of the type of soluble-salt and soluble silicate and precipitating reagent can specifically be carried out according to the prior art
Selection.
For a kind of specific embodiment of the invention, the solubility lanthanum salt can be nitrate, chloride and sulfuric acid
One of salt is a variety of, preferably lanthanum nitrate.
For a kind of specific embodiment of the invention, the soluble-salt of the metallic element M can be nitrate, chlorination
One of object and sulfate are a variety of, preferably nitrate；
For a kind of specific embodiment of the invention, the soluble silicate can be selected from sodium metasilicate, potassium silicate, original
One of sodium metasilicate and potassium orthosilicate are a variety of.
For a kind of specific embodiment of the invention, the precipitating reagent is used to make the sun of silicate ion and soluble-salt
Ionic reaction generates the precipitated cationic of excessive soluble-salt after silicate precipitates.
Under preferable case, the precipitating reagent in weak acid and mild base salt, middle strong acid weak base salt and alkaline matter at least
It is a kind of, wherein the weak acid and mild base salt can be ammonium carbonate and/or ammonium hydrogen carbonate, and the middle strong acid weak base salt can be selected from first
One of sour ammonia, acetic acid ammonia and sulfate of ammoniac are a variety of；The alkaline matter can be selected from ammonium hydroxide, alkali metal hydroxide (such as
Sodium hydroxide and/or potassium hydroxide), soluble carbonate salt (such as sodium carbonate and/or potassium carbonate), amine compounds (such as include but not
Be limited to methylamine and/or ethamine) and alkoxide (as include but is not limited to sodium methoxide) one of or it is a variety of.It is further preferred that in order to enable
What is precipitated is more abundant, and the precipitating reagent uses usually in the form of its aqueous solution.
According to the present invention, precipitation reaction condition includes generally comprising precipitation reaction temperature and precipitation reaction time, wherein excellent
Select precipitation reaction temperature be 10-100 DEG C, more preferably 20-50 DEG C, as long as the precipitation reaction time guarantee reactant sufficiently react simultaneously
Solid sediment is generated, usually can suitably be selected according to practical operation situation.
According to the present invention, under the conditions of precipitation reaction, by soluble lanthanum salt, the soluble-salt of metallic element M and solvable
Property silicate, the mode contacted in water with precipitating reagent can fully obtain lanthanum silicate precipitating and lanthanum/metal M to meet
Hydroxide precipitating and/or lanthanum salt/metal M salt are precipitated as standard.
Under preferable case, in order to which goal of the invention of the invention is better achieved, under the conditions of precipitation reaction, by soluble lanthanum
The soluble-salt and soluble silicate of salt, metallic element M include: with the mode that precipitating reagent contacts in water
It is dissolved in the water the soluble-salt of soluble lanthanum salt, metallic element M to obtain aqueous metal salt, by soluble silicon
Hydrochlorate is dissolved in the water to obtain aqueous silicate solution.Wherein, the typically no special limit of dosage of water in soluble salt solutions is formed
Fixed, lanthanum salt and metallic element M salt can sufficiently be dissolved by being subject to.Under preferable case, the dosage of water can be respectively lanthanum salt or
1-10 times of metal M salt weight.
Mode (1): under stiring, aqueous metal salt being mixed with aqueous silicate solution, obtains reaction mixture, and will
The aqueous solution of precipitating reagent weak acid and mild base salt and/or middle strong acid weak base salt is added in the reaction mixture and is precipitated；Or it will
The aqueous solution of precipitating reagent alkaline matter is added in the reaction mixture and is precipitated, and the pH for controlling obtained precipitated product is
7-14, preferably 8-12, more preferably 9-11；
Wherein, mode aqueous metal salt mixed with aqueous silicate solution is to the no shadow of the acquisition of reaction mixture
It rings, for example, can be that aqueous metal salt is added in aqueous silicate solution, or aqueous silicate solution to be added to
In aqueous metal salt.
Mode (2): under stiring, aqueous metal salt and aqueous silicate solution are added to precipitating reagent weak acid and weak base simultaneously
Precipitation reaction is carried out in the aqueous solution of salt and/or middle strong acid weak base salt, or aqueous metal salt and aqueous silicate solution is same
When be added to the aqueous solution of precipitating reagent alkaline matter and carry out precipitation reaction, and controlling the obtained pH of precipitated product is 7-14, excellent
It is selected as 8-12, more preferably 9-11.
According to the present invention, in the above-mentioned way of contact, it can fully obtain lanthanum silicate precipitating in order to meet, and
Lanthanum/metal M hydroxide precipitating and/or lanthanum salt/metal M salt precipitate, and further include adjusting aqueous metal salt under preferable case
PH value be 0-7, preferably 2-6, more preferably 3-5, and, adjust aqueous silicate solution pH value be 7-14, preferably 8-
12, more preferably 9-11.Wherein, the pH value for adjusting aqueous metal salt and the method for pH value for adjusting aqueous silicate solution are
It is known to one of skill in the art, such as can be adjusted using acid solution or alkaline solution, the acid solution includes
Organic and or inorganic acids, the organic acid include but is not limited to acetic acid and/or benzene sulfonic acid；The inorganic acid includes single unlimited
In one of nitric acid, hydrochloric acid and sulfuric acid or a variety of.The alkaline solution includes organic base and/or inorganic base, the organic base
Including but not limited to methylamine and/or ethamine；The inorganic base includes singly being not limited to one of ammonium hydroxide, NaOH and KOH or a variety of.
According to the present invention, aqueous metal salt is mixed with aqueous silicate solution and revolving speed that precipitating reagent is stirred and
As long as time guarantee sufficiently precipitates and obtain solid sediment, generally, speed of agitator can be 100-1000 revs/min, excellent
It is selected as 150-500 revs/min, mixing time can be 10-180min.Obtained solid sediment is separated from mixing suspension
Method can use various methods well known in the art, it may for example comprise but be not limited to be separated by filtration, be centrifugated.It is preferred that
In the case of, it further include that water is carried out to solid sediment before isolated solid sediment to be dried to (optional) and is roasted
Wash, into water lotion without water soluble ion until.
According to the present invention, condition that is dry and roasting can be selected according to the prior art, for example, drying temperature is
70-120 DEG C, drying time 4-24h；Maturing temperature can be 800-1200 DEG C, calcining time 2-10h.And it is of the invention
Inventors have found that when preparing silicon position doping apatite-type lanthanum silicate using the precipitation method of the invention, even if in lower roasting
At a temperature of roasted the apatite-type lanthanum silicate that pure phase state still can be made, for example, maturing temperature is at 1000 DEG C hereinafter, such as
800-1000 DEG C, it is preferable that calcining time 2-6h.
The present invention also provides the silicon positions of the preparation of the method according to the present invention to adulterate apatite-type lanthanum silicate, the silicon position
Adulterate the general structure of apatite-type lanthanum silicate are as follows: La9.33+xSi6-yMyO26+δ, wherein 0≤x≤0.67,0 < y≤2,0≤δ≤
1, M selected from the IIth A race metal of the periodic table of elements, group IIIA metal, the IVth A race metal, the Ith B race metal, II B-group metal,
At least one of Vth B race metal, group VIB metal, the VIIth B race metal and group VIII metal.Under preferable case, M choosing
From one of Mg, Al, Ga, In, Sn, Ge, Cu, Zn, Nb, W, Mn, Fe, Co, Ni or a variety of, it is more preferably selected from Al, Cu and Fe
One of or it is a variety of.
The present invention also provides the silicon position doping apatite-type lanthanum silicates that the method according to the present invention is prepared to make
Application in standby solid-oxide fuel battery electrolyte.It is being made using silicon position provided by the invention doping apatite-type lanthanum silicate
When standby oxide fuel battery electrolyte, the electrolyte enabled to has superior performance.Wherein, electrolyte is specific
Preparation method can be carried out with reference to the ordinary skill in the art, and details are not described herein.
The present invention will be described in detail by way of examples below.
In following embodiment, all reagents and raw material both can be commercially available, can also be prepared according to existing method.
Embodiment 1
The present embodiment prepares La for illustrating according to the method for the present invention9.33Si5Al1O26(x=0, y=1, δ=0).
Lanthanum nitrate aqueous solution is configured, nitric acid la concn is 15 weight %.Take lanthanum nitrate aqueous solution 142.26g and nine water nitric acid
Aluminium 2.64g, aluminum nitrate are dissolved in wiring solution-forming a after lanthanum nitrate aqueous solution.
Nine water sodium metasilicate 10.0g are taken, are dissolved in 100mL water, and adjusting pH value with dust technology is 9-10, wiring solution-forming b.
Under 300 revs/min of stirring, solution a is added drop-wise in solution b, and the NaOH water of 2mol/L is added dropwise into solution b
Solution is maintained at the pH value of solution b between 9-10.After solution a is all dripped, continue to stir 30min, the pH of products therefrom
Value is 9.5.Product is filtered, and solid is washed three times with deionized water, is then dried for 24 hours at 70 DEG C, then roasted at 900 DEG C
5h is burnt, final product is obtained.
XRD material phase analysis is carried out to product, obtains the pure phase state apatite-type product of silicon position Al doping, XRD spectra is shown in Fig. 1
(wherein, straight line spectrogram is La9.33Si6O26Standard spectrogram, JCPDS No. is 01-074-9552, can be with by spectrogram comparison
It was found that prepared product is pure apatite-type phase).In addition, carrying out elemental analysis to filtered liquid with ICP, it is not detected
Lanthanum and silicon.
Embodiment 2
The present embodiment prepares La for illustrating according to the method for the present invention9.67Si5.5Fe0.5O26.5(x=0.34, y=0.5, δ
=0.5).
Lanthanum nitrate aqueous solution is configured, lanthanum nitrate water concentration is 15 weight %.Take lanthanum nitrate hexahydrate 134.04g and nine water nitric acid
Iron 1.29g, ferric nitrate are dissolved in wiring solution-forming a after lanthanum nitrate aqueous solution.
Nine water sodium metasilicate 10.0g are taken, are dissolved in 100mL water, wiring solution-forming b.
Under 300 revs/min of stirring, solution b is added drop-wise in solution a, after solution b is all dripped, continues to stir
30min, NaOH aqueous solution to the pH value that 2mol/L is then added dropwise is 9.5, is further continued for stirring 30min.Product is filtered, and
Solid is washed three times with deionized water, then in 100 DEG C of baking 6h, then in 950 DEG C of roasting 5h, obtains final product.
XRD material phase analysis is carried out to product, obtains the pure phase state apatite-type product of silicon position Fe doping, XRD spectra is shown in Fig. 2
(wherein, straight line spectrogram is La9.67Si6O26.5Standard spectrogram, JCPDS No. is 98-024-7068, can be with by spectrogram comparison
It was found that prepared product is pure apatite-type phase).In addition, carrying out elemental analysis to filtered liquid with ICP, it is not detected
Lanthanum and silicon.
Embodiment 3
The present embodiment prepares La for illustrating according to the method for the present invention10Si4.5Cu1.5O27(x=0.67, y=1.5, δ=
1)。
Lanthanum nitrate aqueous solution is configured, lanthanum nitrate water concentration is 15 weight %.Take lanthanum nitrate aqueous solution 169.4g and three water nitre
Sour copper 2.83g, copper nitrate are dissolved in wiring solution-forming a after lanthanum nitrate aqueous solution.
Nine water sodium metasilicate 10.0g are taken, are dissolved in 100mL water, wiring solution-forming b.
Under 300 revs/min of stirring, solution b is added drop-wise in solution a, after solution b is all dripped, continues to stir
Then the ammonium bicarbonate aqueous solution of 10 weight % of 100mL is added dropwise in 30min, be further continued for stirring 30min.Centrifugation point is carried out to product
From, and solid is washed three times with deionized water, then in 120 DEG C of baking 4h, then in 1100 DEG C of roasting 4h, obtain final product.
XRD material phase analysis is carried out to product, obtains the pure phase state apatite-type product of silicon position Cu doping, XRD spectra is shown in Fig. 3
(wherein, straight line spectrogram is La10Si6O27Standard spectrogram, JCPDS No. be 00-053-0291, by spectrogram comparison can send out
Existing prepared product is pure apatite-type phase).In addition, carrying out elemental analysis to filtered liquid with ICP, lanthanum is not detected
And silicon.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (10)
1. a kind of preparation method of silicon position doping apatite-type lanthanum silicate, which is characterized in that adulterate apatite-type silicon in the silicon position
The general structure of sour lanthanum are as follows: La9.33+xSi6-yMyO26+δ, wherein 0≤x≤0.67,0 < y≤2,0≤δ≤1, the preparation method
It include: under the conditions of precipitation reaction, according to stoichiometric ratio by soluble lanthanum salt, the soluble-salt of metallic element M and solvable
Property silicate, contacts with precipitating reagent, in water so that soluble silicate respectively sinks the cation of soluble-salt with precipitating reagent
It forms sediment, isolated solid sediment, and the solid sediment is optionally dried, and roasting；
Wherein, metallic element M is selected from the IIth A race metal of the periodic table of elements, group IIIA metal, the IVth A race metal, the Ith B race gold
At least one of category, II B-group metal, the Vth B race metal, group VIB metal, the VIIth B race metal and group VIII metal.
2. preparation method according to claim 1, wherein metallic element M be selected from Mg, Al, Ga, In, Sn, Ge, Cu, Zn,
One of Nb, W, Mn, Fe, Co, Ni or a variety of, preferably one of Al, Cu and Fe or a variety of.
3. preparation method according to claim 1 or 2, wherein
The solubility lanthanum salt is one of nitrate, chloride and sulfate or a variety of；
The soluble-salt of the metallic element M is one of nitrate, chloride and sulfate or a variety of；
The soluble silicate is selected from one of sodium metasilicate, potassium silicate, sodium orthosilicate and potassium orthosilicate or a variety of；
The precipitating reagent is excessive after being used to that the cationoid reaction of silicate ion and soluble-salt to be made to generate silicate precipitates can
The precipitated cationic of soluble；
The precipitating reagent is selected from least one of weak acid and mild base salt, middle strong acid weak base salt and alkaline matter, wherein described weak
Sour weak base salt be ammonium carbonate and/or ammonium hydrogen carbonate, the middle strong acid weak base salt in formic acid ammonia, acetic acid ammonia and sulfate of ammoniac one
Kind is a variety of；The alkaline matter is in ammonium hydroxide, alkali metal hydroxide, soluble carbonate salt, amine compounds and alkoxide
It is one or more.
4. preparation method according to claim 1 or 2, wherein precipitation reaction condition includes: that precipitation reaction temperature is 10-
100 DEG C, preferably 20-50 DEG C.
5. preparation method described in any one of -4 according to claim 1, wherein, will be soluble under the conditions of precipitation reaction
The soluble-salt and soluble silicate of lanthanum salt, metallic element M include: with the mode that precipitating reagent contacts in water
It is dissolved in the water the soluble-salt of soluble lanthanum salt, metallic element M to obtain aqueous metal salt, by soluble silicate
It is dissolved in the water to obtain aqueous silicate solution；
Mode (1): under stiring, aqueous metal salt being mixed with aqueous silicate solution, obtains reaction mixture, and will precipitating
The aqueous solution of agent weak acid and mild base salt and/or middle strong acid weak base salt is added in the reaction mixture and is precipitated；Or it will precipitating
The aqueous solution of agent alkaline matter is added in the reaction mixture and is precipitated, and the pH for controlling obtained precipitated product slurries is
7-14, preferably 8-12, more preferably 9-11；
Mode (2): under stiring, aqueous metal salt and aqueous silicate solution are added to precipitating reagent weak acid and mild base salt simultaneously
And/or precipitation reaction is carried out in the aqueous solution of middle strong acid weak base salt, or simultaneously by aqueous metal salt and aqueous silicate solution
It is added to the aqueous solution progress precipitation reaction of precipitating reagent alkaline matter, and the pH for controlling obtained precipitated product slurries is 7-14,
Preferably 8-12, more preferably 9-11.
6. preparation method according to claim 5, wherein
The pH value for adjusting aqueous metal salt is 0-7, preferably 2-6, more preferably 3-5；
The pH value for adjusting aqueous silicate solution is 7-14, preferably 8-12, more preferably 9-11.
7. method described in any one of -6 according to claim 1, wherein drying temperature is 70-120 DEG C, and drying time is
4-24h；Maturing temperature be 800-1200 DEG C, preferably 900-1000 DEG C, calcining time 2-10h, preferably 2-6h.
8. adulterating apatite-type lanthanum silicate by the silicon position of any one of claim 1-7 the method preparation, which is characterized in that
The general structure of the silicon position doping apatite-type lanthanum silicate are as follows: La9.33+xSi6-yMyO26+δ, wherein 0≤x≤0.67,0 < y≤
2,0≤δ≤1, M are selected from the IIth A race metal of the periodic table of elements, group IIIA metal, the IVth A race metal, the Ith B race metal, the IIth B
At least one of race's metal, the Vth B race metal, group VIB metal, the VIIth B race metal and group VIII metal.
9. apatite-type lanthanum silicate is adulterated in silicon position according to claim 8, wherein M be selected from Mg, Al, Ga, In, Sn, Ge,
One of Cu, Zn, Nb, W, Mn, Fe, Co, Ni or a variety of, preferably one of Al, Cu and Fe or a variety of.
10. being wanted by the silicon position doping apatite-type lanthanum silicate or right of the preparation of any one of claim 1-7 the method
The doping apatite-type lanthanum silicate of silicon position described in asking 8 or 9 is preparing the application in solid-oxide fuel battery electrolyte.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711014347.1A CN109713346A (en) | 2017-10-26 | 2017-10-26 | Adulterate apatite-type lanthanum silicate and its preparation method and application in silicon position |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112029502A (en) * | 2020-08-04 | 2020-12-04 | 盐城工学院 | Lanthanum silicate luminescent powder material with apatite structure and preparation method and application thereof |
| CN115763916A (en) * | 2022-10-24 | 2023-03-07 | 合肥学院 | Ga and Mg co-doped apatite lanthanum silicate solid electrolyte material and preparation method thereof |
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| CN115763916A (en) * | 2022-10-24 | 2023-03-07 | 合肥学院 | Ga and Mg co-doped apatite lanthanum silicate solid electrolyte material and preparation method thereof |
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