CN109704350A - Adulterate apatite-type lanthanum silicate and its preparation method and application in lanthanum position - Google Patents
Adulterate apatite-type lanthanum silicate and its preparation method and application in lanthanum position Download PDFInfo
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Abstract
The present invention relates to field of inorganic materials, a kind of lanthanum position doping apatite-type lanthanum silicate and its preparation method and application, the general structure of the lanthanum position doping apatite-type lanthanum silicate are as follows: La are disclosed9.33+x‑yMySi6O26+δWherein, 0≤x≤0.67,0 < y≤1,0≤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, the Vth A race metal, the Ith B race metal, the Vth B race metal, the VIIth B race metal, group VIII metal and lanthanide series metal in addition to lanthanum.Have the characteristics that phase is pure, at low cost using the lanthanum position doping apatite-type lanthanum silicate of method provided by the invention preparation.
Description
Technical field
The present invention relates to a kind of lanthanum 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 is 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
Journal of Materials Chemistry is offered, 2007,17,2078-2087 proposes a kind of doping of lanthanum position Ca, Sr, Ba
Method, be using lanthana, silica and carbonate as raw material, prepared by solid-state fusion method lanthanum position doping apatite
Type lanthanum silicate.Chinese Journal of Chemical Engineering, 2010,18 (2) 328-332 propose one kind
The method of lanthanum position doping V prepares lanthanum by sol-gel method using lanthanum nitrate, tetraethyl orthosilicate, vanadic anhydride as raw material
The apatite-type lanthanum silicate of position doping.Pass through analysis document discovery, although the cost of material that solid-state fusion method uses is cheap, system
Standby apatite-type electrolyte phase is impure, Chang Hanyou lanthana impurity；Although and sol-gel method can prepare pure phase state
Apatite-type electrolyte, 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 lanthanum position doping phosphorus ash is provided
The preparation method of stone-type lanthanum silicate and lanthanum position obtained by this method doping apatite-type lanthanum silicate and its application, using the present invention
Method pure phase state lanthanum 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 lanthanum position doping apatite-type lanthanum silicate
Method, wherein the general structure of the lanthanum position doping apatite-type lanthanum silicate are as follows: La9.33+x-yMySi6O26+δ, wherein 0≤x≤
0.67,0 < y≤1,0≤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
With precipitating reagent respectively by the precipitated cationic of soluble-salt, isolated solid sediment, and by the solid sediment into
Row is optional dry, and roasting；
Wherein, metallic element M is selected from the IIth A race metal of the periodic table of elements, the Vth A race metal, the Ith B race metal, the Vth B
At least one of race's metal, the VIIth B race metal, group VIII metal and lanthanide series metal in addition to lanthanum.
Second aspect of the present invention provides the lanthanum position doping apatite-type silicic acid for stating a kind of preparation of the method according to the present invention
Lanthanum, wherein the general structure of the lanthanum position doping apatite-type lanthanum silicate are as follows: La9.33+x-yMySi6O26+δ, wherein 0≤x≤
0.67,0 < y≤1,0≤δ≤1, M are selected from the IIth A race metal of the periodic table of elements, the Vth A race metal, the Ith B race metal, the Vth B race
At least one of metal, the VIIth B race metal, group VIII metal and lanthanide series metal in addition to lanthanum.
It is solid in preparation that the third aspect of the present invention provides a kind of lanthanum 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 lanthanum position using the precipitation method with cheap silicate
Apatite-type lanthanum silicate, preparation method is simple, and maturing temperature is low, and the lanthanum 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 lanthanum position prepared by the embodiment of the present invention 1；
Fig. 2 is the XRD diagram of doping apatite-type lanthanum silicate in lanthanum position prepared by the embodiment of the present invention 2；
Fig. 3 is the XRD diagram of doping apatite-type lanthanum silicate in lanthanum 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 lanthanum position doping apatite-type lanthanum silicate provided according to the present invention, wherein adulterate phosphorus in the lanthanum position
The general structure of grey stone-type lanthanum silicate are as follows: La9.33+x-yMySi6O26+δ, wherein 0≤x≤0.67,0 < y≤1,0≤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, the Vth A race metal, the Ith B race metal, the Vth B
At least one of race's metal, the VIIth B race metal, group VIII metal and lanthanide series metal in addition to lanthanum.
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 lanthanum 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 lanthanum 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, Ca, Sr, Ba, Co, Ni, Cu, Mn, Bi, V, Nd, Sm, Gd and Yb
One of or it is a variety of, be more preferably selected from one of Mn, Ba and Sr 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 manganese nitrate, what the cation of the soluble-salt referred to
It is manganese ion (generally Mn2+).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 lanthanum position doping apatite-type lanthanum silicate general structure
The soluble-salt and soluble silicate of soluble lanthanum salt, metallic element M are taken, and is contacted in water with precipitating reagent, so that can
Soluble silicate and precipitating reagent are optionally done isolated solid sediment respectively by the precipitated cationic of soluble-salt
It is dry and roast and can be realized the purpose of the present invention, in the present invention, the solubility lanthanum salt, metallic element M soluble-salt and
Optional wider range of the type of soluble silicate and precipitating reagent, can specifically be selected according to the prior art.
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, preferably heavy
Shallow lake reaction temperature be 10-100 DEG C, more preferably 20-50 DEG C, as long as the precipitation reaction time guarantee reactant sufficiently react and generate
Solid sediment 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 lanthanum 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 be 1000 DEG C hereinafter, such as
800-1000 DEG C, it is preferable that calcining time 2-6h.
The present invention also provides the lanthanum positions of the preparation of the method according to the present invention to adulterate apatite-type lanthanum silicate, the lanthanum position
Adulterate the general structure of apatite-type lanthanum silicate are as follows: La9.33+x-yMySi6O26+δ, wherein 0≤x≤0.67,0 < y≤1,0≤δ≤
1, M selected from the IIth A race metal of the periodic table of elements, the Vth A race metal, the Ith B race metal, the Vth B race metal, the VIIth B race metal,
At least one of group VIII metal and the lanthanide series metal in addition to lanthanum.Under preferable case, M be selected from Mg, Ca, Sr, Ba, Co,
One of Ni, Cu, Mn, Bi, V, Nd, Sm, Gd and Yb or a variety of are more preferably selected from one of Mn, Ba and Sr or a variety of.
The present invention also provides the lanthanum 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 lanthanum 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 invention8.83Mn0.5Si6O26(x=0, y=0.5, δ=0).
Lanthanum nitrate aqueous solution is configured, lanthanum nitrate water concentration is 15 weight %.Take lanthanum nitrate aqueous solution 112.2g and 50 weights
Measure % manganese nitrate aqueous solution 1.05g, wiring solution-forming a after manganese nitrate aqueous solution is mixed with 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.At 300 revs/min
Under stirring, solution a is added drop-wise in solution b, and the NaOH aqueous solution of 2mol/L is added dropwise into solution b, protects the pH value of solution b
It holds between 9-10.After solution a is all dripped, continue to stir 30min, the pH value of products therefrom is 9.5.Product is taken out
Filter, and solid is washed three times with deionized water, it is then dried for 24 hours at 70 DEG C, then in 900 DEG C of roasting 5h, obtain final product.
XRD material phase analysis is carried out to product, obtains the pure phase state apatite-type product of lanthanum position Mn doping, XRD spectra is shown in Fig. 1
(straight line spectrogram is La9.33Si6O26Standard spectrogram, JCPDS No. is 01-074-9552, by spectrogram comparison it can be found that institute
Preparing product is pure apatite-type phase).In addition, carry out elemental analysis to filtered liquid with ICP, be not detected lanthanum and
Silicon.
Embodiment 2
The present embodiment prepares La for illustrating according to the method for the present invention8.66Ba1Si6O26.5(x=0.33, y=1.0, δ=
0.5)。
Lanthanum nitrate aqueous solution is configured, lanthanum nitrate water concentration is 15 weight %.Take lanthanum nitrate aqueous solution 110.2g and barium nitrate
1.53g, barium 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 10 weight % ammonium carbonate solution of 100mL is added dropwise in 30min, be further continued for stirring 30min.Product is filtered, is used in combination
Deionized water washes solid three times, 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 lanthanum position Ba doping, XRD spectra is shown in Fig. 2
(straight line spectrogram is La9.67Si6O26.5Standard spectrogram, JCPDS No. be 98-024-7068, by spectrogram comparison it can be found that
Prepared product is pure apatite-type phase).In addition, carry out elemental analysis to filtered liquid with ICP, be not detected lanthanum and
Silicon.
Embodiment 3
The present embodiment prepares La for illustrating according to the method for the present invention9.8Sr0.2Si6O27(x=0.67, y=0.2, δ=
1)。
Lanthanum nitrate hexahydrate is configured, lanthanum nitrate water concentration is 15 weight %.Take lanthanum nitrate aqueous solution 124.5g and strontium nitrate
0.25g is dissolved in strontium nitrate in lanthanum nitrate aqueous solution, wiring solution-forming a.
Nine water sodium metasilicate 10.0g are taken, are dissolved in 100mL water, wiring solution-forming b.
Under 300 revs/min of stirring, solution a is added drop-wise in solution b.After solution a is all dripped, continue to stir
30min, then 10 weight % ammonium bicarbonate aqueous solution of 100mL is added dropwise into suspension, continue to stir 30min.Product is taken out
Filter, and solid is washed three times with deionized water, it is then dried for 24 hours at 70 DEG C, then in 1200 DEG C of roasting 5h, obtain final product.
XRD material phase analysis is carried out to product, obtains the pure phase state apatite-type product of lanthanum position Sr doping, XRD spectra is shown in Fig. 3
(straight line spectrogram is La10Si6O27Standard spectrogram, JCPDS No. is 00-053-0291, by spectrogram comparison it can be found that made
Standby product is pure apatite-type phase).In addition, carrying out elemental analysis to filtered liquid with ICP, lanthanum and silicon is not detected.
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 lanthanum position doping apatite-type lanthanum silicate, which is characterized in that adulterate apatite-type silicon in the lanthanum position
The general structure of sour lanthanum are as follows: La9.33+x-yMySi6O26+δ, wherein 0≤x≤0.67,0 < y≤1,0≤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, the Vth A race metal, the Ith B race metal, the Vth B race gold
At least one of category, the VIIth B race metal, group VIII metal and the lanthanide series metal in addition to lanthanum.
2. preparation method according to claim 1, wherein metallic element M be selected from Mg, Ca, Sr, Ba, Co, Ni, Cu, Mn,
One of Bi, V, Nd, Sm, Gd and Yb or a variety of are preferably selected from one of Mn, Ba and Sr 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 lanthanum position of any one of claim 1-7 the method preparation, which is characterized in that
The general structure of the lanthanum position doping apatite-type lanthanum silicate are as follows: La9.33+x-yMySi6O26+δ, wherein 0≤x≤0.67,0 < y≤
1,0≤δ≤1, M are selected from the IIth A race metal of the periodic table of elements, the Vth A race metal, the Ith B race metal, the Vth B race metal, the VIIth B
At least one of race's metal, group VIII metal and lanthanide series metal in addition to lanthanum.
9. apatite-type lanthanum silicate is adulterated in lanthanum position according to claim 8, wherein M be selected from Mg, Ca, Sr, Ba, Co, Ni,
One of Cu, Mn, Bi, V, Nd, Sm, Gd and Yb or a variety of are preferably selected from one of Mn, Ba and Sr or a variety of.
10. being wanted by the lanthanum 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 lanthanum position described in asking 8 or 9 is preparing the application in solid-oxide fuel battery electrolyte.
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| CN201711019397.9A CN109704350A (en) | 2017-10-26 | 2017-10-26 | Adulterate apatite-type lanthanum silicate and its preparation method and application in lanthanum position |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110808395A (en) * | 2019-11-12 | 2020-02-18 | 武汉工程大学 | Neodymium and zinc co-doped apatite lanthanum silicate solid electrolyte and preparation method thereof |
| 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 |
| CN114699561A (en) * | 2021-12-30 | 2022-07-05 | 佛山市中医院 | Calcium-doped material, bone repair material and preparation method thereof |
| CN115710125A (en) * | 2022-11-21 | 2023-02-24 | 武汉纺织大学 | Preparation method of low dielectric microwave dielectric ceramic material with adjustable color |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101028929A (en) * | 2005-11-17 | 2007-09-05 | J.M.休伯有限公司 | Method of removing heavy metal from silicate source during silicate manufacturing |
| CN101615679A (en) * | 2009-07-29 | 2009-12-30 | 华南理工大学 | Vanadium-doped in lanthanum site apatite-type lanthanum silicate solid electrolyte and preparation method thereof |
-
2017
- 2017-10-26 CN CN201711019397.9A patent/CN109704350A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101028929A (en) * | 2005-11-17 | 2007-09-05 | J.M.休伯有限公司 | Method of removing heavy metal from silicate source during silicate manufacturing |
| CN101615679A (en) * | 2009-07-29 | 2009-12-30 | 华南理工大学 | Vanadium-doped in lanthanum site apatite-type lanthanum silicate solid electrolyte and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| YANGZHOU MA ET AL: "Novel chemical reaction co-precipitation method for the synthesis of apatite-type lanthanum silicate as an electrolyte in SOFC", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| 卢小瑞: "掺杂Al硅酸镧电解质的制备、表征及电性能研究", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110808395A (en) * | 2019-11-12 | 2020-02-18 | 武汉工程大学 | Neodymium and zinc co-doped apatite lanthanum silicate solid electrolyte and preparation method thereof |
| 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 |
| CN112029502B (en) * | 2020-08-04 | 2023-07-07 | 盐城工学院 | Lanthanum silicate luminescent powder material with apatite structure, and preparation method and application thereof |
| CN114699561A (en) * | 2021-12-30 | 2022-07-05 | 佛山市中医院 | Calcium-doped material, bone repair material and preparation method thereof |
| CN115710125A (en) * | 2022-11-21 | 2023-02-24 | 武汉纺织大学 | Preparation method of low dielectric microwave dielectric ceramic material with adjustable color |
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Application publication date: 20190503 |