CN102044700B - Lithium lanthanum bismuthate-based solid electrolyte material and preparation method thereof - Google Patents

Lithium lanthanum bismuthate-based solid electrolyte material and preparation method thereof Download PDF

Info

Publication number
CN102044700B
CN102044700B CN2009101849151A CN200910184915A CN102044700B CN 102044700 B CN102044700 B CN 102044700B CN 2009101849151 A CN2009101849151 A CN 2009101849151A CN 200910184915 A CN200910184915 A CN 200910184915A CN 102044700 B CN102044700 B CN 102044700B
Authority
CN
China
Prior art keywords
lanthanum
lithium
bismuth
solid electrolyte
electrolyte material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN2009101849151A
Other languages
Chinese (zh)
Other versions
CN102044700A (en
Inventor
高云霞
王先平
王伟国
阚志鹏
庄重
程帜军
方前锋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hefei Institutes of Physical Science of CAS
Original Assignee
Hefei Institutes of Physical Science of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hefei Institutes of Physical Science of CAS filed Critical Hefei Institutes of Physical Science of CAS
Priority to CN2009101849151A priority Critical patent/CN102044700B/en
Publication of CN102044700A publication Critical patent/CN102044700A/en
Application granted granted Critical
Publication of CN102044700B publication Critical patent/CN102044700B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Landscapes

  • Conductive Materials (AREA)
  • Secondary Cells (AREA)

Abstract

The present invention discloses Lithium lanthanum bismuthate-based solid electrolyte material and preparation method thereof. The chemical formula of the material of Lithium lanthanum bismuthate-based solid electrolyte after the doping of lanthanum and the doping of lithium are conducted is La(3-x)AxLi(5+delta)Bi(2-y)ByO12. In the formula, A is the lanthanum position dopant, X is a value from 0 to 1.25, B is the bismuth position dopant, and Y is a value from 0 to 1.25. The preparation method of the material is as follows: according to the formula, weighing nitrates or carbonates or chlorides or acetates or alkoxides or oxides soluble in acids of lithium, lanthanum, bismuth, the lanthanum-position dopant and/or the bismuth-position dopant, preparing a solution by using the above chemicals, adding a lanthanum salt solution, a bismuth solution, a solution of lanthanum-position dopant and/or a solution of bismuth-position dopant dropwisely, adding citric acid and nitric acid successively to obtain a sol, adding a water-soluble polymer into the sol to form a gel, drying the gel, performing heat treatment to obtain nanocrystal powder, moulding the powder into a green body, and calcining to obtain the Lithium lanthanum bismuthate-based solid electrolyte material. The prepared material can be used as a solid electrolyte material and can be applied to all-solid-lithium ion battery.

Description

Lithium lanthanum bismuthate-based solid electrolyte material and preparation method thereof
Technical field
The present invention relates to a kind of solid electrolyte material and preparation method, especially a kind of lithium lanthanum bismuthate-based solid electrolyte material and preparation method thereof.
Background technology
The all solid state lithium ion battery is the lithium ion battery of new generation that immediate development is got up, compare with present business-like lithium battery, have easy microminiaturization, security performance good, be convenient to processing, without advantages such as inner pressure of battery, can effectively eliminate the safety issues such as the traditional liquid electrolyte lithium-ion battery is inflammable, volatile, electrolyte is easily revealed, heat resistance is poor, and be expected to adopt lithium metal as negative pole, improve widely the specific capacity of battery.Therefore, all solid state lithium ion battery is expected to require the field of high security to be with a wide range of applications at microelectronic component, microsensor etc.At present, people have done some trials and effort in order to obtain all solid state lithium ion battery, once disclose a kind of lanthanium titanate lithium and analog thereof such as " lithium inorganic solid electrolyte " literary composition in " chemical progress " the 15th volume the 2nd phase magazine of publishing in March, 2003.This have the lanthanium titanate lithium of perovskite structure and the lithium inorganic solid electrolyte material of similar structures exists weak point, at first, although the bulk conductivity in the time of 25 ℃ reaches 10 -3S/cm can be comparable with at present practical polymeric liquid electrolyte, but its grain boundary resistance only is 10 up to 50 times of volume resistance thereby cause the total conductivity under the room temperature -5The S/cm magnitude; Secondly, electrochemical stability is relatively poor, and when it was directly contacted with lithium metal, redox reaction can occur for both, causes Ti 4+Be reduced into Ti 3+, thereby higher electronic conductivity appears, therefore be not suitable as the electrolyte in all solid state lithium ion battery; Again, the synthesis temperature for preparing it is too high, reaches 1300 ℃, and high like this preparation synthesis temperature has caused a large amount of losses of lithia, and so that the component of titanium, lanthanum and lithium is difficult for control.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of electrochemical stability good lithium lanthanum bismuthate-based solid electrolyte material for overcoming weak point of the prior art.
The preparation method of the lithium lanthanum bismuthate-based solid electrolyte material that another technical problem that the present invention will solve synthesis temperature when be provided a kind of the preparation is low.
For solving technical problem of the present invention, the technical scheme that adopts is: lithium lanthanum bismuthate-based solid electrolyte material comprises having La 3Li 5Bi 2O 12The bismuthic acid lanthanum lithium base that chemical formula forms, particularly,
Chemical formula after mixing in the lanthanum position of described bismuthic acid lanthanum lithium base and bismuth position consists of La 3-XA XLi 5+ δBi 2-YB YO 12A in the chemical formula is lanthanum position alloy, it is barium (Ba) or calcium (Ca) or potassium (K) or rare earth element, x is 0～1.25, B is bismuth position alloy, it is indium (In) or vanadium (V) or tantalum (Ta) or niobium (Nb) or antimony (Sb), and y is 0～1.25.
As the further improvement of lithium lanthanum bismuthate-based solid electrolyte material, described La 3-XA XLi 5+ δBi 2-YB YO 12Crystal grain diameter be 2～10 μ m; Described rare earth element is praseodymium (Pr) or neodymium (Nd) or yttrium (Y) or cerium (Ce) or samarium (Sm) or gadolinium (Gd).
For solving another technical problem of the present invention, another technical scheme that adopts is: the preparation method of lithium lanthanum bismuthate-based solid electrolyte material comprises sol-gel process, and particularly completing steps is as follows,
Step 1 is according to La 3-XA XLi 5+ δBi 2-YB YO 12The composition ratio, take by weighing the lithium of respective amount, lanthanum, bismuth, the nitrate of lanthanum position alloy and/or bismuth position alloy or carbonate or chloride or acetate or alkoxide or soluble oxide in acid, and with its add respectively be mixed with corresponding solution in the solvent after, first to placing 30～100 ℃, drip the lanthanum salting liquid in the lithium salt solution under stirring, the bismuth salting liquid, lanthanum position alloy solution and/or bismuth position alloy solution, obtain the mixed solution that the metal ion total concentration is 0.1～10mol/L, stir after adding citric acid in the mixed solution again, wherein, the mol ratio of the total metal ion in citric acid and the mixed solution is 0.5～2: 1, then, to wherein adding after the nitre acid for adjusting pH value is 0.5～5, be placed on 30～100 ℃ of lower 1～2h of stirring, obtain the colloidal sol of transparent clear;
Step 2, add high molecular weight water soluble polymer in the colloidal sol after, be placed on and be stirred to the formation gel under 30～100 ℃, wherein, the mass ratio of high molecular weight water soluble polymer and citric acid is 1～2: 1～40;
Step 3, first gel is placed 80～100 ℃ of lower dry 22～26h, obtain fluffy xerogel, again xerogel is placed 600～800 ℃ of lower heat treatment 2～10h, obtain nanocrystalline powder, then, first nanocrystalline powder is molded into base substrate, be placed on again 730～800 ℃ of lower calcining 5～10h, make lithium lanthanum bismuthate-based solid electrolyte material.
As the preparation method's of lithium lanthanum bismuthate-based solid electrolyte material further improvement, described solvent is water or ethanol or ethylene glycol or aforementioned two or more mixed liquor; Described corresponding solution is corresponding settled solution; Described high molecular weight water soluble polymer is polyethylene glycol or polyvinyl alcohol or polyvinylpyrrolidone; Described mold pressing is that single shaft is pressed, and the pressure of its shaping is 150～600MPa; Described heating rate when being warming up to 600～800 ℃ of heat treatment is 0.5～4 ℃/min; The crystal grain diameter of described nanocrystalline powder is 50～200nm.
Beneficial effect with respect to prior art is, one, use respectively field emission scanning electron microscope and x-ray diffractometer to characterize to the product that makes, by its result as can be known, the crystal grain diameter of product is 2～10 μ m, the bismuthic acid lanthanum lithium base that product is mixed by lanthanum position and/or bismuth position consists of, and the chemical formula after the doping consists of La 3-XA XLi 5+ δBi 2-YB YO 12, the A in the chemical formula is lanthanum position alloy, and it is barium or calcium or potassium or rare earth element, and x is that 0～1.25, B is bismuth position alloy, and it is indium or vanadium or tantalum or niobium or antimony, and y is 0～1.25, and rare earth element is praseodymium or neodymium or yttrium or cerium or samarium or gadolinium.Bismuthic acid lanthanum lithium is typical garnet structure; Its two, after tested, product total conductivity at room temperature is 10 -5～10 -4S/cm improves with respect to the room temperature total conductivity of the lithium inorganic solid electrolyte material of existing lanthanium titanate lithium and similar structures, does not also find that its existence is similar to simultaneously to cause Ti with the lithium metal reaction in the lanthanium titanate lithium 4+Be reduced into Ti 3+And the phenomenon of generation electronic conductance; Its three, heat treatment and the temperature of calcining of preparation during product is low, only up to 800 ℃, this can not cause a large amount of losses of lithia far below 1300 ℃, thereby so that the component of titanium, lanthanum and lithium very easily control; Its four, doping process is easy to easily and accurately control the chemical composition of product, realizes easily the doping of various compositions and content, the time of heat treatment and calcining is short, operating process is convenient, is suitable for large-scale industrial production.
As the further embodiment of beneficial effect, the one, La 3-XA XLi 5+ δBi 2-YB YO 12Crystal grain diameter be preferably 2～10 μ m, be beneficial to it and be used for all solid state lithium ion battery as solid electrolyte material; The 2nd, doped with rare-earth elements is preferably praseodymium or neodymium or yttrium or cerium or samarium or gadolinium, both so that the source of raw material than horn of plenty, makes again preparation technology more easily implement and flexibly; The 3rd, solvent is preferably water or ethanol or ethylene glycol or aforementioned two or more mixed liquor, high molecular weight water soluble polymer is preferably polyethylene glycol or polyvinyl alcohol or polyvinylpyrrolidone, not only make the selection of solvent and high molecular weight water soluble polymer that the larger room for maneuver has been arranged, also be beneficial to the preparation of product; The 4th, the pressure of single shaft die forming is preferably 150～600MPa, all is easy to the formation of product.
Description of drawings
Below in conjunction with accompanying drawing optimal way of the present invention is described in further detail.
Fig. 1 uses field emission scanning electron microscope (SEM) to observe one of SEM photo of taking behind the pattern to the numerous intermediate-nanocrystalline powders that make and product.Wherein, Fig. 1 a and Fig. 1 b are the SEM photo of nanocrystalline powder, can be found out by it, and the particle diameter of nanocrystalline powder is more even, and its crystal grain diameter is 50～200nm.Fig. 1 c and Fig. 1 d are the SEM photo of product, can be found out by it, and the crystal grain diameter of product is 2～10 μ m.
Fig. 2 uses one of XRD spectra that obtains after the test of X-ray diffraction (XRD) instrument to the numerous products that make.From this XRD spectra as can be known, product is for being doped with the lithium lanthanum bismuthate-based solid electrolyte material of calcium in the lanthanum position.
Fig. 3 uses one of AC impedance spectrogram that obtains after the alternating current impedance instrument test to the numerous products that make.Grain resistance and the grain boundary resistance of product under probe temperature can be obtained by this AC impedance spectrogram by match, then the conductivity value that obtains product can be transformed by following formula
σ = l S ( R gi + R gb ) ,
L in the formula is product thickness, and S is the electrode area on product surface, R GiBe grain resistance, R GbBe grain boundary resistance.
Embodiment
At first make or buy from market nitrate, carbonate, chloride, acetate, alkoxide and the soluble oxide acid of lithium, lanthanum, bismuth, lanthanum position alloy and bismuth position alloy with conventional method, lanthanum position alloy wherein is barium, calcium, potassium and rare earth element, bismuth position alloy is indium, vanadium, tantalum, niobium and antimony, rare earth element is praseodymium, neodymium, yttrium, cerium, samarium and gadolinium, as water, ethanol, ethylene glycol and the aforementioned two or more mixed liquor of solvent, as polyethylene glycol, polyvinyl alcohol and the polyvinylpyrrolidone of high molecular weight water soluble polymer.Then,
Embodiment 1
The concrete steps of preparation are:
Step 1 is according to La 3-XA XLi 5+ δBi 2-YB YO 12The composition ratio, x wherein is 0, y is 1.25, take by weighing the nitrate of lithium, lanthanum, bismuth and bismuth position alloy of respective amount or carbonate or chloride or acetate or alkoxide or in acid soluble oxide, and with its add respectively be mixed with corresponding solution in the solvent after; Wherein, lithium, lanthanum, bismuth and bismuth position alloy are its nitrate, are specially lithium nitrate, lanthanum nitrate, bismuth nitrate and indium nitrate, and solvent is water, and corresponding solution is corresponding settled solution.First to placing 30 ℃, stirring lower lithium salt solution dropping lanthanum salting liquid, bismuth salting liquid and bismuth position alloy solution, wherein, lithium salt solution is that lithium nitrate solution, lanthanum salting liquid are that lanthanum nitrate hexahydrate, bismuth salting liquid are that bismuth nitrate solution, bismuth position alloy solution are indium nitrate solution, obtains the mixed solution that the metal ion total concentration is 0.1mol/L.Stir after adding citric acid in the mixed solution again, wherein, the mol ratio of the total metal ion in citric acid and the mixed solution is 0.5: 1.Then, to wherein adding after the nitre acid for adjusting pH value is 0.5, be placed on 30 ℃ of lower 2h of stirring, obtain the colloidal sol of transparent clear.
Step 2, add high molecular weight water soluble polymer in the colloidal sol after, be placed on and be stirred to the formation gel under 30 ℃; Wherein, the mass ratio of high molecular weight water soluble polymer and citric acid is 1: 40, and high molecular weight water soluble polymer is polyethylene glycol.
Step 3 places gel first 80 ℃ of lower dry 26h, obtains fluffy xerogel, xerogel is placed 600 ℃ of lower heat treatment 10h again; Wherein, the heating rate when being warming up to 600 ℃ of heat treatment is 0.5 ℃/min, obtains being similar to the nanocrystalline powder shown in Fig. 1 a and Fig. 1 b.Then, first nanocrystalline powder is molded into base substrate; Wherein, mold pressing is that single shaft is pressed, and the pressure of its shaping is 150MPa.Be placed on again 730 ℃ of lower calcining 10h, make and be similar to shown in Fig. 1 c and Fig. 1 d, and be similar to the lithium lanthanum bismuthate-based solid electrolyte material shown in the curve among Fig. 2 and Fig. 3.
Embodiment 2
The concrete steps of preparation are:
Step 1 is according to La 3-XA XLi 5+ δBi 2-YB YO 12The composition ratio, x wherein is 0.1, y is 0.8, take by weighing the nitrate of lithium, lanthanum, bismuth, lanthanum position alloy and bismuth position alloy of respective amount or carbonate or chloride or acetate or alkoxide or in acid soluble oxide, and with its add respectively be mixed with corresponding solution in the solvent after; Wherein, lithium, lanthanum, bismuth, lanthanum position alloy and bismuth position alloy are its nitrate, are specially lithium nitrate, lanthanum nitrate, bismuth nitrate, calcium nitrate and indium nitrate, and solvent is water, and corresponding solution is corresponding settled solution.First to placing 50 ℃, stirring lower lithium salt solution dropping lanthanum salting liquid, bismuth salting liquid, lanthanum position alloy solution and bismuth position alloy solution, wherein, lithium salt solution is that lithium nitrate solution, lanthanum salting liquid are that lanthanum nitrate hexahydrate, bismuth salting liquid are that bismuth nitrate solution, lanthanum position alloy solution are that calcium nitrate solution, bismuth position alloy solution are indium nitrate solution, obtains the mixed solution that the metal ion total concentration is 0.8mol/L.Stir after adding citric acid in the mixed solution again, wherein, the mol ratio of the total metal ion in citric acid and the mixed solution is 0.8: 1.Then, to wherein adding after the nitre acid for adjusting pH value is 1, be placed on 50 ℃ of lower 1.8h of stirring, obtain the colloidal sol of transparent clear.
Step 2, add high molecular weight water soluble polymer in the colloidal sol after, be placed on and be stirred to the formation gel under 50 ℃; Wherein, the mass ratio of high molecular weight water soluble polymer and citric acid is 1.2: 30, and high molecular weight water soluble polymer is polyethylene glycol.
Step 3 places gel first 85 ℃ of lower dry 25h, obtains fluffy xerogel, xerogel is placed 650 ℃ of lower heat treatment 8h again; Wherein, the heating rate when being warming up to 650 ℃ of heat treatment is 1 ℃/min, obtains being similar to the nanocrystalline powder shown in Fig. 1 a and Fig. 1 b.Then, first nanocrystalline powder is molded into base substrate; Wherein, mold pressing is that single shaft is pressed, and the pressure of its shaping is 250MPa.Be placed on again 750 ℃ of lower calcining 9h, make and be similar to shown in Fig. 1 c and Fig. 1 d, and be similar to the lithium lanthanum bismuthate-based solid electrolyte material shown in the curve among Fig. 2 and Fig. 3.
Embodiment 3
The concrete steps of preparation are:
Step 1 is according to La 3-XA XLi 5+ δBi 2-YB YO 12The composition ratio, x wherein is 0.5, y is 0, take by weighing the nitrate of lithium, lanthanum, bismuth and lanthanum position alloy of respective amount or carbonate or chloride or acetate or alkoxide or in acid soluble oxide, and with its add respectively be mixed with corresponding solution in the solvent after; Wherein, lithium, lanthanum, bismuth and lanthanum position alloy are its nitrate, are specially lithium nitrate, lanthanum nitrate, bismuth nitrate and calcium nitrate, and solvent is water, and corresponding solution is corresponding settled solution.First to placing 65 ℃, stirring lower lithium salt solution dropping lanthanum salting liquid, bismuth salting liquid and lanthanum position alloy solution, wherein, lithium salt solution is that lithium nitrate solution, lanthanum salting liquid are that lanthanum nitrate hexahydrate, bismuth salting liquid are that bismuth nitrate solution, lanthanum position alloy solution are calcium nitrate solution, obtains the mixed solution that the metal ion total concentration is 3mol/L.Stir after adding citric acid in the mixed solution again, wherein, the mol ratio of the total metal ion in citric acid and the mixed solution is 1.2: 1.Then, to wherein adding after the nitre acid for adjusting pH value is 3, be placed on 65 ℃ of lower 1.5h of stirring, obtain the colloidal sol of transparent clear.
Step 2, add high molecular weight water soluble polymer in the colloidal sol after, be placed on and be stirred to the formation gel under 65 ℃; Wherein, the mass ratio of high molecular weight water soluble polymer and citric acid is 1.5: 20, and high molecular weight water soluble polymer is polyethylene glycol.
Step 3 places gel first 90 ℃ of lower dry 24h, obtains fluffy xerogel, xerogel is placed 700 ℃ of lower heat treatment 6h again; Wherein, the heating rate when being warming up to 700 ℃ of heat treatment is 2 ℃/min, obtains the nanocrystalline powder shown in Fig. 1 a and Fig. 1 b.Then, first nanocrystalline powder is molded into base substrate; Wherein, mold pressing is that single shaft is pressed, and the pressure of its shaping is 350MPa.Be placed on again 765 ℃ of lower calcining 8h, make shown in Fig. 1 c and Fig. 1 d, and the lithium lanthanum bismuthate-based solid electrolyte material shown in the curve among Fig. 2 and Fig. 3.
Embodiment 4
The concrete steps of preparation are:
Step 1 is according to La 3-XA XLi 5+ δBi 2-YB YO 12The composition ratio, x wherein is 0.8, y is 0.4, take by weighing the nitrate of lithium, lanthanum, bismuth, lanthanum position alloy and bismuth position alloy of respective amount or carbonate or chloride or acetate or alkoxide or in acid soluble oxide, and with its add respectively be mixed with corresponding solution in the solvent after; Wherein, lithium, lanthanum, bismuth, lanthanum position alloy and bismuth position alloy are its nitrate, are specially lithium nitrate, lanthanum nitrate, bismuth nitrate, calcium nitrate and indium nitrate, and solvent is water, and corresponding solution is corresponding settled solution.First to placing 80 ℃, stirring lower lithium salt solution dropping lanthanum salting liquid, bismuth salting liquid, lanthanum position alloy solution and bismuth position alloy solution, wherein, lithium salt solution is that lithium nitrate solution, lanthanum salting liquid are that lanthanum nitrate hexahydrate, bismuth salting liquid are that bismuth nitrate solution, lanthanum position alloy solution are that calcium nitrate solution, bismuth position alloy solution are indium nitrate solution, obtains the mixed solution that the metal ion total concentration is 7mol/L.Stir after adding citric acid in the mixed solution again, wherein, the mol ratio of the total metal ion in citric acid and the mixed solution is 1.6: 1.Then, to wherein adding after the nitre acid for adjusting pH value is 4.5, be placed on 80 ℃ of lower 1.2h of stirring, obtain the colloidal sol of transparent clear.
Step 2, add high molecular weight water soluble polymer in the colloidal sol after, be placed on and be stirred to the formation gel under 80 ℃; Wherein, the mass ratio of high molecular weight water soluble polymer and citric acid is 1.8: 10, and high molecular weight water soluble polymer is polyethylene glycol.
Step 3 places gel first 95 ℃ of lower dry 23h, obtains fluffy xerogel, xerogel is placed 750 ℃ of lower heat treatment 4h again; Wherein, the heating rate when being warming up to 750 ℃ of heat treatment is 3 ℃/min, obtains being similar to the nanocrystalline powder shown in Fig. 1 a and Fig. 1 b.Then, first nanocrystalline powder is molded into base substrate; Wherein, mold pressing is that single shaft is pressed, and the pressure of its shaping is 500MPa.Be placed on again 780 ℃ of lower calcining 6h, make and be similar to shown in Fig. 1 c and Fig. 1 d, and be similar to the lithium lanthanum bismuthate-based solid electrolyte material shown in the curve among Fig. 2 and Fig. 3.
Embodiment 5
The concrete steps of preparation are:
Step 1 is according to La 3-XA XLi 5+ δBi 2-YB YO 12The composition ratio, x wherein is 1.25, y is 0.1, take by weighing the nitrate of lithium, lanthanum, bismuth, lanthanum position alloy and bismuth position alloy of respective amount or carbonate or chloride or acetate or alkoxide or in acid soluble oxide, and with its add respectively be mixed with corresponding solution in the solvent after; Wherein, lithium, lanthanum, bismuth, lanthanum position alloy and bismuth position alloy are its nitrate, are specially lithium nitrate, lanthanum nitrate, bismuth nitrate, calcium nitrate and indium nitrate, and solvent is water, and corresponding solution is corresponding settled solution.First to placing 100 ℃, stirring lower lithium salt solution dropping lanthanum salting liquid, bismuth salting liquid, lanthanum position alloy solution and bismuth position alloy solution, wherein, lithium salt solution is that lithium nitrate solution, lanthanum salting liquid are that lanthanum nitrate hexahydrate, bismuth salting liquid are that bismuth nitrate solution, lanthanum position alloy solution are that calcium nitrate solution, bismuth position alloy solution are indium nitrate solution, obtains the mixed solution that the metal ion total concentration is 10mol/L.Stir after adding citric acid in the mixed solution again, wherein, the mol ratio of the total metal ion in citric acid and the mixed solution is 2: 1.Then, to wherein adding after the nitre acid for adjusting pH value is 5, be placed on 100 ℃ of lower 1h of stirring, obtain the colloidal sol of transparent clear.
Step 2, add high molecular weight water soluble polymer in the colloidal sol after, be placed on and be stirred to the formation gel under 100 ℃; Wherein, the mass ratio of high molecular weight water soluble polymer and citric acid is 2: 1, and high molecular weight water soluble polymer is polyethylene glycol.
Step 3 places gel first 100 ℃ of lower dry 22h, obtains fluffy xerogel, xerogel is placed 800 ℃ of lower heat treatment 2h again; Wherein, the heating rate when being warming up to 800 ℃ of heat treatment is 4 ℃/min, obtains being similar to the nanocrystalline powder shown in Fig. 1 a and Fig. 1 b.Then, first nanocrystalline powder is molded into base substrate; Wherein, mold pressing is that single shaft is pressed, and the pressure of its shaping is 600MPa.Be placed on again 800 ℃ of lower calcining 5h, make and be similar to shown in Fig. 1 c and Fig. 1 d, and be similar to the lithium lanthanum bismuthate-based solid electrolyte material shown in the curve among Fig. 2 and Fig. 3.
Select respectively again lithium, lanthanum, bismuth, the nitrate of lanthanum position alloy and bismuth position alloy or carbonate or chloride or acetate or alkoxide or soluble oxide in acid, lanthanum position alloy wherein is barium or calcium or potassium or rare earth element, bismuth position alloy is indium or vanadium or tantalum or niobium or antimony, rare earth element is praseodymium or neodymium or yttrium or cerium or samarium or gadolinium, carrying out the doping of lanthanum position or the doping of bismuth position or dibit mixes, water or ethanol or ethylene glycol or aforementioned two or more mixed liquor as solvent, polyethylene glycol or polyvinyl alcohol or polyvinylpyrrolidone as high molecular weight water soluble polymer, repeat above-described embodiment 1～5, make equally as or be similar to shown in Figure 1, and as or be similar to the lithium lanthanum bismuthate-based solid electrolyte material shown in the curve among Fig. 2 and Fig. 3.
Obviously, those skilled in the art can carry out various changes and modification to lithium lanthanum bismuthate-based solid electrolyte material of the present invention and preparation method thereof and not break away from the spirit and scope of the present invention.Like this, if of the present invention these are revised and modification belongs within the scope of claim of the present invention and equivalent technologies thereof, then the present invention also is intended to comprise these changes and modification interior.

Claims (9)

1. a lithium lanthanum bismuthate-based solid electrolyte material comprises and intends it is carried out the La that has of doping treatment 3Li 5Bi 2O 12The basic configuration of the bismuthic acid lanthanum lithium base that chemical formula forms is characterized in that:
Chemical formula after mixing in the lanthanum position of described bismuthic acid lanthanum lithium base and bismuth position consists of La 3-XA XLi 5+ δBi 2-YB YO 12, the A in the chemical formula is lanthanum position alloy, and it is barium or calcium or potassium or rare earth element, and x is that 0～1.25, B is bismuth position alloy, and it is indium or vanadium or tantalum or niobium or antimony, y is 0～1.25.
2. lithium lanthanum bismuthate-based solid electrolyte material according to claim 1 is characterized in that La 3-XA XLi 5+ δBi 2-YB YO 12Crystal grain diameter be 2～10 μ m.
3. lithium lanthanum bismuthate-based solid electrolyte material according to claim 1 is characterized in that rare earth element is praseodymium, or neodymium, or yttrium, or cerium, or samarium, or gadolinium.
4. the preparation method of the described lithium lanthanum bismuthate-based solid electrolyte material of claim 1 comprises sol-gel process, it is characterized in that completing steps is as follows:
Step 1 is according to La 3-XA XLi 5+ δBi 2-YB YO 12The composition ratio, take by weighing the lithium of respective amount, lanthanum, bismuth, the nitrate of lanthanum position alloy and/or bismuth position alloy or carbonate or chloride or acetate or alkoxide or soluble oxide in acid, and with its add respectively be mixed with corresponding solution in the solvent after, first to placing 30～100 ℃, drip the lanthanum salting liquid in the lithium salt solution under stirring, the bismuth salting liquid, lanthanum position alloy solution and/or bismuth position alloy solution, obtain the mixed solution that the metal ion total concentration is 0.1～10mol/L, stir after adding citric acid in the mixed solution again, wherein, the mol ratio of the total metal ion in citric acid and the mixed solution is 0.5～2: 1, then, to wherein adding after the nitre acid for adjusting pH value is 0.5～5, be placed on 30～100 ℃ of lower 1～2h of stirring, obtain the colloidal sol of transparent clear;
Step 2, add high molecular weight water soluble polymer in the colloidal sol after, be placed on and be stirred to the formation gel under 30～100 ℃, wherein, the mass ratio of high molecular weight water soluble polymer and citric acid is 1～2: 1～40;
Step 3, first gel is placed 80～100 ℃ of lower dry 22～26h, obtain fluffy xerogel, again xerogel is placed 600～800 ℃ of lower heat treatment 2～10h, obtain nanocrystalline powder, then, first nanocrystalline powder is molded into base substrate, be placed on again 730～800 ℃ of lower calcining 5～10h, make lithium lanthanum bismuthate-based solid electrolyte material.
5. the preparation method of lithium lanthanum bismuthate-based solid electrolyte material according to claim 4 is characterized in that solvent is water, or ethanol, or ethylene glycol, or aforementioned two or more mixed liquor.
6. the preparation method of lithium lanthanum bismuthate-based solid electrolyte material according to claim 4 is characterized in that high molecular weight water soluble polymer is polyethylene glycol, or polyvinyl alcohol, or polyvinylpyrrolidone.
7. the preparation method of lithium lanthanum bismuthate-based solid electrolyte material according to claim 4 is characterized in that mold pressing is that single shaft is pressed, and the pressure of its shaping is 150～600MPa.
8. the preparation method of lithium lanthanum bismuthate-based solid electrolyte material according to claim 4, the heating rate when it is characterized in that being warming up to 600～800 ℃ of heat treatment is 0.5～4 ℃/min.
9. the preparation method of lithium lanthanum bismuthate-based solid electrolyte material according to claim 4, the crystal grain diameter that it is characterized in that nanocrystalline powder is 50～200nm.
CN2009101849151A 2009-10-19 2009-10-19 Lithium lanthanum bismuthate-based solid electrolyte material and preparation method thereof Expired - Fee Related CN102044700B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2009101849151A CN102044700B (en) 2009-10-19 2009-10-19 Lithium lanthanum bismuthate-based solid electrolyte material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2009101849151A CN102044700B (en) 2009-10-19 2009-10-19 Lithium lanthanum bismuthate-based solid electrolyte material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN102044700A CN102044700A (en) 2011-05-04
CN102044700B true CN102044700B (en) 2013-03-27

Family

ID=43910628

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2009101849151A Expired - Fee Related CN102044700B (en) 2009-10-19 2009-10-19 Lithium lanthanum bismuthate-based solid electrolyte material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN102044700B (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103594726B (en) * 2013-10-15 2016-01-20 中南大学 Garnet structure tantalic acid lanthanum lithium based solid electrolyte material and preparation method thereof
CN106803601B (en) * 2017-02-26 2019-12-13 合肥国轩高科动力能源有限公司 preparation method of solid electrolyte lithium lanthanum titanium oxide film
WO2018226826A1 (en) * 2017-06-06 2018-12-13 The Regents Of The University Of Michigan Method for suppressing metal propagation in solid electrolytes
CN107910574B (en) * 2017-11-15 2020-04-17 白强 Preparation method of composite solid electrolyte for fuel cell
CN108511797B (en) * 2018-05-09 2022-07-19 哈尔滨工业大学（威海） Li7La3Zr2O12Solid electrolyte preparation method
CN109742442A (en) * 2018-12-24 2019-05-10 北京化工大学 The secondary cell of the preparation and application of the Garnet-type solid electrolyte solid electrolyte
RU2704990C1 (en) * 2019-07-09 2019-11-01 Федеральное государственное бюджетное учреждение науки Институт химии твердого тела Уральского отделения Российской академии наук Lanthanum and calcium complex lithium tantalate producing method
CN115775689B (en) * 2022-11-02 2023-11-24 深圳江浩电子有限公司 Solid polymer electrolyte, preparation method and solid-liquid mixed capacitor

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009152014A (en) * 2007-12-19 2009-07-09 Tokyo Institute Of Technology Solid oxide cell
CN100539288C (en) * 2004-12-02 2009-09-09 株式会社小原 All solid state type lithium rechargeable battery and solid electrolyte thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100539288C (en) * 2004-12-02 2009-09-09 株式会社小原 All solid state type lithium rechargeable battery and solid electrolyte thereof
JP2009152014A (en) * 2007-12-19 2009-07-09 Tokyo Institute Of Technology Solid oxide cell

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
郑子山等.锂无机固体电解质.《化学进展》.2003,第15卷(第2期),101-106. *

Also Published As

Publication number Publication date
CN102044700A (en) 2011-05-04

Similar Documents

Publication Publication Date Title
CN102044700B (en) Lithium lanthanum bismuthate-based solid electrolyte material and preparation method thereof
Tang et al. Potassium vanadates with stable structure and fast ion diffusion channel as cathode for rechargeable aqueous zinc-ion batteries
Chirayil et al. Hydrothermal synthesis of vanadium oxides
CN105990563B (en) Secondary lithium battery, positive electrode material thereof and preparation method of positive electrode material
JP6393974B2 (en) Solid electrolyte precursor, method for producing the same, method for producing the solid electrolyte, and method for producing the solid electrolyte-electrode active material composite
CN102088085B (en) Lithium ion battery positive material and preparation method thereof
CN106299352A (en) The preparation method of positive pole material of secondary lithium battery
CN104710302B (en) Oxalic acid ferrimanganic presoma of grade doping and preparation method thereof
CN101635348B (en) Tantalum-containing lithium ion battery cathode material lithium titanate preparation method
CN103594726B (en) Garnet structure tantalic acid lanthanum lithium based solid electrolyte material and preparation method thereof
CN105977486B (en) A kind of preparation method and application of the rich sodium transition metal silicate as sodium-ion battery positive material
CN107848894A (en) Carbuncle type oxidate sintered body and its manufacture method
CN101348279B (en) Lanthanum molybdate based solid electrolyte film material and preparation thereof
CN105118983B (en) Method for preparing lithium nickel manganese oxide anode material
CN101630732A (en) Nanoscale lithium titanate compound and preparation method thereof
CN105655573B (en) A kind of general preparative methods of the adjustable one-dimensional micro-nano structure manganese base lithium ion battery electrode material of draw ratio
CN105024067B (en) Lithium ion battery, composite doped modified positive active material thereof and preparation method
CN107017405A (en) A kind of anode material for lithium-ion batteries and preparation method thereof
CN102295312B (en) Tungsten-doped vanadium dioxide nanopowder and preparation method for the same
CN107546384B (en) Lithium ion battery cathode material with disordered rock salt structure and preparation method thereof
CN107651706A (en) A kind of preparation method of bismuthic acid lanthanum nanometer rods
CN103078120A (en) Ferrous silicate lithium ion battery cathode material with hierarchical structure and preparation method
Cheng et al. A novel electrolyte for intermediate solid oxide fuel cells
Cheng et al. Synthesis and electrical properties of scheelite Ca1− xSmxMoO4+ δ solid electrolyte ceramics
CN104779387B (en) Lithium ion battery LiNi1-x-yCoxAlyO2The preparation method of material

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20130327

Termination date: 20151019

EXPY Termination of patent right or utility model