CN109540874A - The method for detecting inorganic element content in the sample of lithium lanthanum zirconium oxygen type solid electrolyte - Google Patents
The method for detecting inorganic element content in the sample of lithium lanthanum zirconium oxygen type solid electrolyte Download PDFInfo
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Abstract
The invention proposes the methods of inorganic element content in the sample of detection lithium lanthanum zirconium oxygen type solid electrolyte, which includes: that (1) carries out melting processing to sample, adds hydrofluoric acid and carries out filtration treatment, to obtain filtrate and filter residue；(2) alkali fusion processing is carried out to filter residue, and hydrochloric acid solution is added, to obtain the solution of filter residue；(3) assay of inorganic elements is carried out respectively to the solution of filtrate and filter residue using inductive coupling plasma emission spectrograph.Detection method proposed by the invention, can detect that the content of lithium, lanthanum, zirconium in lithium lanthanum zirconium oxygen type solid state electrolysis quality sample by inductive coupling plasma emission spectrograph, and data accuracy is higher, easy to operate and more rapidly efficient.
Description
Technical field
The present invention relates to technical field of analytical chemistry, specifically, the present invention relates to detection lithium lanthanum zirconium oxygen type solid electrolytes
Sample in inorganic element content method.
Background technique
Since lithium ion battery is commercialized since 1991, have always been considered as be most prospect chemical energy storage equipment.However,
Organic liquid electrolytes inflammability, leakage and easily it is dendrites, brought safety problem hinders lithium ion battery big
Huge advantage in terms of type energy storage.But inorganic solid electrolyte has superior chemistry, mechanical and thermal stability, Yi Ji electricity
The many advantages such as a possibility that pond minimizes.
Wherein, the Li of garnet structure7La3Zr2O12(LLZO), due to total ionic conductivity with higher, excellent change
And thermal stability, especially its stability to lithium metal, become a kind of ideal lithium ion battery solid electrolyte.Pomegranate
Stone structure belongs to tetrahedron and octahedra mixed matrix structure, therefore, adjusts skeleton knot using the method for changing compound composition
Structure can be changed ion fast transferring bottleneck size, and enhances the migration of lithium ion, to derive a variety of with Doped ions
LLZO compound, wherein Li7-xLa3Zr2-xTaxO12It (LLZTO) is the Zr Typical Representatives adulterated, it is vertical with carbuncle type
Square structure, and its room-temperature conductivity is up to 6.1 × 10-4S·cm-1。
But at this stage in novel solid electrolyte material this for LLZO type compound inorganic element content survey
Examination, temporarily there are no disclosed document report or testing standards.
Summary of the invention
The present invention is the following discovery based on inventor and completes:
The present inventor has found in the course of the research, at present to inorganic element content in LLZO type solid electrolyte
Measuring method mainly has chemical analysis, atomic absorption method, X fluorescence spectrum method and inductive coupling plasma emission spectrograph method
Deng.Wherein, the cumbersome of chemical analysis, reagent dosage are larger, analytical cycle is long and inorganic elements between have it is mutually dry
Disturb and influence the accuracy of test；Atomic absorption spectrography (AAS) is suitble to the analysis of single element, test condition needed for different elements
It is entirely different, and test process is cumbersome, and high temperature resistant element zirconium (Zr), tantalum (Ta) test the N used2O-C2H2N in flame2O is deposited
In higher risk, and the test effect of Zr, Ta are also unsatisfactory；Moreover, though X fluorescence spectrum method is suitable for test lanthanum
(La), the content of zirconium (Zr) and tantalum (Ta), but it is not particularly suited for the content measuring of light metal lithium (Li), and equipment is expensive, maintenance
At high cost, when carrying out quantitative test, the Matrix Match degree of working curve and sample is required very high.
The present inventor, which passes through further investigation, also found, cube phase structure of the LLZO type solid electrolyte such as LLZTO
It is highly stable, it is difficult to be dissolved in the inorganic acids such as hydrochloric acid, nitric acid, chloroazotic acid or hydrofluoric acid under normal temperature and pressure, meanwhile, zirconium, the tantalum of high-content
It is easily hydrolyzed again in non-hydrofluoric medium, although can be stabilized in hydrofluoric medium, lanthanum (La) and hydrofluoric acid knot
Conjunction will form lanthanum fluoride precipitating instead.So above-mentioned reason result in LLZO type solid electrolyte be difficult it is complete in same medium
It is measured while pairs of lithium, lanthanum, zirconium and tantalum.Therefore, inventor uses the sample of high-temperature fusion LLZO type solid electrolyte, then uses
Hydrofluoric acid precipitation and separation goes out lanthanum, then filtrates tested and the content of at least one of lithium, lanthanum, zirconium and tantalum in precipitating respectively, most
Adduction can calculate the total content of each inorganic elements afterwards.
In view of this, an object of the present invention is to provide one kind can detect LLZO type solid-state electricity by ICP-OES
Solve that lithium lanthanum zirconium content, data accuracy in quality sample be higher, easy to operate or more efficient method.
In the first aspect of the present invention, the invention proposes nothings in a kind of sample for detecting lithium lanthanum zirconium oxygen type solid electrolyte
The method of machine constituent content.
According to an embodiment of the invention, the inorganic elements includes at least one of lithium, lanthanum and zirconium, the method packet
It includes: (1) melting processing being carried out to the sample, add hydrofluoric acid and carry out filtration treatment, to obtain filtrate and filter residue；(2)
Alkali fusion processing is carried out to the filter residue, and hydrochloric acid solution is added, to obtain the solution of the filter residue；(3) inductive coupling etc. is utilized
Ionomer emission spectrum instrument to the solution of the filtrate and the filter residue, carries out the assay of the inorganic elements respectively.
Using the detection method of the embodiment of the present invention, the sample of lithium lanthanum zirconium oxygen type solid electrolyte is melted and precipitating is added
After agent hydrofluoric acid, lanthanum can be effectively separated, then the filter residue being settled out is melted, then the solution of filtrate and filter residue is examined respectively
The content of at least one of lithium, lanthanum and zirconium is surveyed, in this way, detecting lithium lanthanum zirconium simultaneously by inductive coupling plasma emission spectrograph
The content of lithium lanthanum zirconium in oxygen type solid state electrolysis quality sample, data accuracy are higher, easy to operate and more rapidly efficient.
In addition, detection method according to the above embodiment of the present invention, can also have the following additional technical features:
According to an embodiment of the invention, the lithium lanthanum zirconium oxygen type solid electrolyte is lithium lanthanum zirconium tantalum oxygen solid electrolyte, institute
Stating inorganic elements includes at least one of lithium, lanthanum, zirconium and tantalum.
According to an embodiment of the invention, melting processing includes: (1-1) by the sample and natrium carbonicum calcinatum, borax
Mixing, then it is warming up under 900~1100 degrees Celsius melting 15~cool down after sixty minutes；(1-2) is into the melt after cooling
Ultrapure water, hydrochloric acid is added, is extracted under 150~250 degrees Celsius.
According to an embodiment of the invention, the weight ratio of the sample and the natrium carbonicum calcinatum, the borax be 3:(60~
100): (30~50), and the weight ratio of the natrium carbonicum calcinatum and the borax is 2:1.
According to an embodiment of the invention, the step of addition hydrofluoric acid includes: (1-3), to melt that treated molten to described
The hydrofluoric acid is added in liquid, heating reaction 10~30 minutes under 150~250 degrees Celsius, and stand and be not less than 0.5 hour.
According to an embodiment of the invention, including: (1-4) filtration treatment in the step of filtration treatment, to obtain filtrate
And filter residue；The filtrate is moved to constant volume in the volumetric flask of 100mL and forms solution by (1-5)；(1-6) pipettes solution described in 10mL
The constant volume into the volumetric flask of 50mL, to obtain the first solution to be measured.
According to an embodiment of the invention, alkali fusion processing, which includes: (2-1), carries out ashing processing to the filter residue, then plus
Enter sodium peroxide, and is melted 5~20 minutes under 600~700 degrees Celsius.
According to an embodiment of the invention, described the step of hydrochloric acid solution is added includes: the molten of (2-2) Xiang Suoshu alkali fusion processing
Ultrapure water, hydrochloric acid are added in liquid, is extracted under 150~250 degrees Celsius, the solution of the extraction is moved to the appearance of 500mL
Constant volume in measuring bottle, to obtain the second solution to be measured.
According to an embodiment of the invention, the step of assay of the inorganic elements includes: (3-1) in the inorganic member
Under the corresponding Detection wavelength of element, inductively coupled plasma is carried out to the described first solution to be measured and second solution to be measured respectively
The test of body emission spectrum；(3-2) calculates the inductively coupled plasma spectrometry according to the standard curve of the inorganic elements
The sum of the content of the result of the test inorganic elements accordingly.
According to an embodiment of the invention, the Detection wavelength is 670 ± 1nm when the inorganic elements is lithium；It is described inorganic
When element is lanthanum, the Detection wavelength is 379 ± 1nm；When the inorganic elements is zirconium, the Detection wavelength is 339 ± 1nm；
When the inorganic elements is tantalum, the Detection wavelength is 240 ± 1nm.
According to an embodiment of the invention, when the inorganic elements is selected from least one of lithium, zirconium and tantalum, it is described inorganic
The standard curve of element is a series of inorganic member that various concentrations are tested by inductive coupling plasma emission spectrograph
What the mixed standard solution of element determined.
According to an embodiment of the invention, the standard curve of the inorganic elements is to pass through electricity when the inorganic elements is lanthanum
What the standard solution that sense coupled plasma optical emission spectrometer tests a series of inorganic elements of various concentrations determined.
Additional aspect and advantage of the invention will be set forth in part in the description, and will partially become from the following description
Obviously, or practice through the invention is recognized.
Detailed description of the invention
Above-mentioned aspect combination following accompanying drawings of the invention explains the description of embodiment, in which:
Fig. 1 is the detection method flow diagram of one embodiment of the invention；
Fig. 2 is the flow diagram of the detection method of another embodiment of the present invention.
Specific embodiment
The embodiment of the present invention is described below in detail, those skilled in the art is it will be appreciated that following example is intended for solving
The present invention is released, and is not construed as limitation of the present invention.Unless stated otherwise, it is not expressly recited in embodiment below specific
Technology or conditions, those skilled in the art can be according to common technology or conditions in the art or according to product description
It carries out.
In one aspect of the invention, the invention proposes nothings in a kind of sample for detecting lithium lanthanum zirconium oxygen type solid electrolyte
The method of machine constituent content.It should be noted that " lithium lanthanum zirconium oxygen (LLZO) type solid electrolyte " herein specifically refers to
There is the solid electrolyte containing elements such as lithium, lanthanum, zirconium, oxygen of garnet structure, includes the lithium lanthanum with other Doped ions
Zirconium oxygen compound, specifically such as lithium lanthanum zirconium tantalum oxygen (LLZTO), etc..
According to an embodiment of the invention, detectable inorganic elements include in lithium (Li), lanthanum (La) and zirconium (Zr) extremely
Few one kind, specific inorganic elements type those skilled in the art can be according to the specific of lithium lanthanum zirconium oxygen type solid electrolyte to be measured
Type is correspondingly selected.In some embodiments of the invention, lithium lanthanum zirconium oxygen type solid electrolyte can be lithium lanthanum zirconium tantalum
Oxygen (LLZTO) solid electrolyte, in this way, detectable inorganic elements correspondingly includes lithium (Li), lanthanum (La), zirconium (Zr) and tantalum
At least one of (Ta).
According to an embodiment of the invention, with reference to Fig. 1, which includes:
S100: carrying out melting processing to sample, adds hydrofluoric acid and carries out filtration treatment, to obtain filtrate and filter residue.
In this step, sample melting is handled, adds hydrofluoric acid, and filtration treatment can get filtrate and filter residue.Its
In, Li and Ta in lithium lanthanum zirconium oxygen type solid electrolyte are mainly distributed in filtrate, and La and the Zr of a part are in hydrofluoric acid
Precipitating is formd, mainly with LaF3Form and Na2ZrF6Form be separated from hydrofluoric acid.
According to an embodiment of the invention, the specific method that processing is melted in step S100 is not particularly limited, this field
Technical staff can correspondingly be selected according to the specific type of lithium lanthanum zirconium oxygen type solid electrolyte.In some implementations of the invention
In example, with reference to Fig. 2, step S100 can include:
S110: sample is mixed with natrium carbonicum calcinatum, borax, reheats cooling after melting.
In this step, the sample of lithium lanthanum zirconium oxygen type solid electrolyte is mixed with natrium carbonicum calcinatum, borax, then be warming up to
Under 900~1100 degrees Celsius melting 15~cool down after sixty minutes, in this way, can pyrolytic lithium lanthanum zirconium oxygen (LLZO) type compound.
In some embodiments of the invention, for the sample of lithium lanthanum zirconium tantalum oxygen (LLZTO), after being mixed with natrium carbonicum calcinatum, borax,
It is cooling after being warming up to 1000 degrees Celsius of meltings 30 minutes, in this way, the melting processing using above-mentioned condition can effectively decompose lithium lanthanum
Zirconium tantalum oxygen solid electrolyte.
According to an embodiment of the invention, the specific ratio of sample and natrium carbonicum calcinatum, borax is not particularly limited, ability
Field technique personnel can correspondingly be adjusted according to the specific type of lithium lanthanum zirconium oxygen type solid electrolyte.In some realities of the invention
Apply in example, the weight ratio of sample and natrium carbonicum calcinatum, borax can be 3:(60~100): (30~50), and natrium carbonicum calcinatum and boron
The weight ratio of sand can be 2:1, in this way, can be under 900~1100 degrees Celsius effectively by lithium lanthanum zirconium oxygen type solid electrolyte high temperature
It decomposes.In some specific examples, for the sample of lithium lanthanum zirconium tantalum oxygen (LLZTO), the weight of sample and natrium carbonicum calcinatum, borax
Weight ratio than that can be 3:80:40 and natrium carbonicum calcinatum and borax is 2:1, in this way, can be under 1000 degrees Celsius effectively by lithium
Lanthanum zirconium tantalum oxygen solid electrolyte decomposes.
S120: ultrapure water, hydrochloric acid being added into melt after cooling, reheat and extract.
In this step, ultrapure water, hydrochloric acid is added to the melt after cooling of step S110, and at 150~250 degrees Celsius
Under extract, in this way, excessive hydrochloric acid solution is solvable to solve Li+。
According to an embodiment of the invention, the specific reactive mode being added after hydrofluoric acid in step S100 is not limited particularly
System, those skilled in the art can correspondingly be selected according to the specific type of lithium lanthanum zirconium oxygen type solid electrolyte.In the present invention
Some embodiments in, with reference to Fig. 2, step S100 can further comprise:
S130: being added hydrofluoric acid to melting in treated melt, heating, which is reacted, simultaneously to be stood.
In this step, hydrofluoric acid, the lanthanum fluoride of formation can be added in the hydrochloric acid solution that step S120 is obtained
(LaF3) precipitate and may separate out lanthanum, and heating reaction 10~30 minutes under 150~250 degrees Celsius, and stand and be not less than
0.5 hour, in this way, the lanthanum in hydrochloric acid solution can be made sufficiently to react with excessive hydrofluoric acid.In some embodiments of the invention,
For the sample of lithium lanthanum zirconium tantalum oxygen (LLZTO), hydrofluoric acid can be added after melting processing, and heating reaction at 200 degrees celsius
20 minutes, in this way, the Li in lithium lanthanum zirconium tantalum oxygen solid electrolyte out can effectively be dissolved+、Ta5+。
According to an embodiment of the invention, the specific method of the filtration treatment in step S100 is not particularly limited, ability
Field technique personnel can correspondingly be selected according to the specific partial size precipitated in hydrofluoric acid solution.In some embodiments of the present invention
In, with reference to Fig. 2, after the step of hydrofluoric acid is added, step S100 can further comprise:
S140: filtration treatment, to obtain filtrate and filter residue.
In this step, the solution after hydrofluoric acid reaction step S130 can be added is filtered processing, in this way, can will contain
There is Li+Hydrochloric acid and hydrofluoric acid filtrate with there are LaF3And Na2ZrF6Filter residue separation.In some embodiments of the invention,
For the sample of lithium lanthanum zirconium tantalum oxygen (LLZTO), precipitating can be kept completely separate using Medium speed filter paper, in this way, can get Li+、Ta5+
Hydrochloric acid and hydrofluoric acid filtrate, and there are LaF3And Na2ZrF6Filter residue.
It in some embodiments of the invention, can be to step in order to obtain more accurate ICP-OES test result with reference to Fig. 2
Filtrate after rapid S140 filtration treatment carries out the preparation of following steps:
S150: filtrate is moved into wiring solution-forming in volumetric flask.
In this step, the filtrate of step S140 filtration treatment is moved into constant volume in the volumetric flask of 100mL, and is formed molten
Liquid.Specifically, the filtrate of filtration treatment can be directly collected into the plastics volumetric flask of 100mL, add ultrapure water and constant volume,
It shakes up.
S160: pipetting the solution of part into volumetric flask, is made into the first solution to be measured.
In this step, constant volume again is pipetted in the volumetric flask of 10mL to 50mL, from the solution that step S150 is obtained to obtain
Obtain the first solution to be measured.Specifically, the plastics volumetric flask of 10mL to 50mL can be pipetted from the 100mL solution after first time constant volume
In, it adds ultrapure water and carries out second of constant volume, shakes up, first so obtained solution to be measured is surveyed for subsequent ICP-OES
Examination.
S200: alkali fusion processing is carried out to filter residue, and hydrochloric acid solution is added, to obtain the solution of filter residue.
In this step, alkali fusion processing is carried out to the filtered filter residue of step S100, adds hydrochloric acid solution, can be filtered
The solution of slag, in this way, for LaF present in filter residue3And Na2ZrF6Alkali fusion is handled again, be can get and is dissolved in hydrochloric acid solution
La3+、Zr4+。
According to an embodiment of the invention, the specific method that the alkali fusion in step S200 is handled is not particularly limited, ability
Field technique personnel can correspondingly be selected according to the concrete composition of filter residue.In some embodiments of the invention, with reference to Fig. 2,
Step S200 can include:
S210: ashing processing is carried out to filter residue, adds sodium peroxide, and melt.
In this step, ashing processing can be carried out to the step S140 filter residue obtained, adds sodium peroxide (Na2O2), and
It is melted 5~20 minutes under 600~700 degrees Celsius, in this way, the precipitating high temperature alkali fuse in filter residue can be decomposed.Of the invention
In some embodiments, for the sample of lithium lanthanum zirconium tantalum oxygen (LLZTO), the Medium speed filter paper with filter residue can be subjected to ashing processing,
Only retain sediment to remove filter paper, adds excessive Na2O2It is carried out alkali fusion 10 minutes under 650 degrees Celsius, it can be effective
The abundant alkali fusion of filter residue after ground melts lithium lanthanum zirconium tantalum oxygen solid electrolyte decomposes.
According to an embodiment of the invention, the concrete mode of the addition hydrochloric acid solution in step S200 is not particularly limited,
Those skilled in the art can correspondingly be selected according to actual dissolution situation after hydrochloric acid solution is added.Of the invention some
In embodiment, with reference to Fig. 2, step S200 can further comprise:
S220: ultrapure water, hydrochloric acid are added in the melt handled to alkali fusion and extracts, the solution of extraction is moved in volumetric flask
It is made into the second solution to be measured.
In this step, ultrapure water, hydrochloric acid are added into step S210 alkali fusion treated melt, then 150~250
It is extracted under degree Celsius, then the solution of extraction is moved in the Glass capacity bottle of 500mL and carry out constant volume, shaken up, to obtain the
Two solution to be measured.
S300: using inductive coupling plasma emission spectrograph respectively to the solution of filtrate and filter residue, inorganic member is carried out
The assay of element.
In this step, by inductive coupling plasma emission spectrograph (ICP-OES), respectively to the filter of step S100
The solution of the filter residue of liquid and S200 carries out the assay of inorganic elements.In some embodiments of the invention, with reference to Fig. 2, step
Rapid S300 can include:
S310: under the corresponding Detection wavelength of inorganic elements, the first solution to be measured and the second solution to be measured are carried out respectively
Inductively coupled plasma atomic emission test.
In this step, the suitable Detection wavelength of inorganic elements is selected, it is to be measured molten to the first solution to be measured and second respectively
Liquid carries out ICP-OES test.According to an embodiment of the invention, the specific Detection wavelength in ICP-OES test process, this field
Technical staff can correspondingly be selected according to the specific type of inorganic elements to be measured, specific for example, when inorganic elements is lithium pair
The Detection wavelength answered is 670 ± 1nm, and corresponding Detection wavelength is 379 ± 1nm when inorganic elements is lanthanum, when inorganic elements is zirconium
Corresponding Detection wavelength is 339 ± 1nm, and corresponding Detection wavelength is 240 ± 1nm, etc. when inorganic elements is tantalum, in this way,
The spectral intensity of the lithium, lanthanum, zirconium or the tantalum that detect under suitable Detection wavelength is more acurrate.
S320: according to the standard curve of inorganic elements, the result for calculating inductively coupled plasma spectrometry test is corresponding
The sum of the content of inorganic elements.
In this step, according to the standard curve of inorganic elements, the ICP-OES test result for calculating step S310 is corresponding
The sum of the content of inorganic elements.Specifically, by taking zr element as an example a series of zirconium standard solution can be pre-configured with, then in phase
ICP-OES test successively is carried out to the zirconium standard solution of various concentration under same Detection wavelength, it is corresponding according to each zirconium concentration
Spectral intensity on spectrogram can draw out the standard curve of zr element；Exist further according to the first solution to be measured and the second solution to be measured
Respective ICP-OES spectral intensity under identical Detection wavelength calculates corresponding zirconium concentration from standard curve respectively, then will
Zirconium content in filtrate and filter residue sums up, and can be obtained the total content of zirconium in the sample of lithium lanthanum zirconium oxygen type solid electrolyte.
According to an embodiment of the invention, the preparation method of the standard curve of inorganic elements is not particularly limited, it can be with one
Its standard solution is fabricated separately out in kind inorganic elements, and a variety of inorganic elements can also be made by mixing out to standard solution, this field skill
Art personnel can correspondingly be designed according to the inorganic elements type being primarily present in filtrate during actual test and filter residue.
In some embodiments of the invention, when inorganic elements is selected from least one of lithium, zirconium and tantalum, inorganic elements
Standard curve can be a series of various concentrations (specifically microgram/milli of such as 0,5,10,15,20 and 25 is tested by ICP-OES
Rise etc.) above-mentioned inorganic elements mixed standard solution determine.In this way, need to only change detection wave for same standard solution
Length can carry out ICP-OES test to different inorganic elements, so as to shorten the time for obtaining standard curve.
In some embodiments of the invention, when inorganic elements is lanthanum, the standard curve of inorganic elements, which can be, to be passed through
ICP-OES tests a series of mark of the inorganic elements of various concentrations (specifically such as 0,10,20,30,40 and 50 mcg/mls)
What quasi- solution determined.In this way, carrying out ICP-OES to the standard solution of various concentration under same Detection wavelength for lanthanum element
Test, can accurately obtain the standard curve of lanthanum.
According to an embodiment of the invention, inorganic in sample in order to more accurately detect lithium lanthanum zirconium oxygen type solid electrolyte
The content of element, the content of substrate can be consistent with solution to be measured in the standard solution of preparation, specifically, inorganic elements with it is anhydrous
Sodium carbonate, borax weight ratio can be 3:(60~100): (30~50), and the weight ratio of natrium carbonicum calcinatum and borax can be 2:
1, etc., in this way, the content of substrate in standard solution can be made close with solution to be measured, such as the hybrid standard of lithium, zirconium and tantalum is molten
The content of substrate is close with the first solution to be measured in liquid, and the content of substrate and the second solution phase to be measured in the standard solution of lanthanum
Closely, so as to keeping the inorganic element content in calculated filtrate and filter residue more acurrate.
In conclusion according to an embodiment of the invention, the invention proposes a kind of detection method, by lithium lanthanum zirconium oxygen type solid-state
After the sample of electrolyte melts and precipitating reagent hydrofluoric acid is added, lanthanum can be effectively separated, then the filter residue being settled out is melted, so
The content for detecting at least one of lithium, lanthanum and zirconium respectively to the solution of filtrate and filter residue afterwards, in this way, passing through inductively coupled plasma
Body emission spectrometer can detect that the content of lithium, lanthanum, zirconium in lithium lanthanum zirconium oxygen type solid state electrolysis quality sample, and data accuracy is more
It is high, easy to operate and more rapidly efficient.
Below with reference to specific embodiment, present invention is described, it should be noted that these embodiments are only descriptive
, without limiting the invention in any way.
Instrument and raw material
Instrument: 7400 inductive coupling plasma emission spectrograph of iCAP, it is public purchased from U.S. Thermo Scientific
Department；Smart Plus-N ultrapure water machine is purchased from Shanghai power health；Muffle furnace is purchased from West Beijing nit.
Raw material: Li, La, Zr, Ta single element standard solution, concentration 1000ug/mL, purchased from national steel material test
Heart Iron and Steel Research Geueral Institute；Natrium carbonicum calcinatum-borax mixed flux, excellent pure grade, sodium carbonate and borax are 2:1 in mass ratio；Peroxide
Change sodium, analyzes pure；HCl, HF are MOS grades；Testing water used is ultrapure water, and resistivity is 18.2M Ω cm.
Embodiment 1
In this embodiment, Li is detected7-xLa3Zr2-xTaxO12(LLZTO) in the sample of solid electrolyte Li, La, Zr and
Ta content.The specific method is as follows:
(a) sample of 0.1000g is weighed in platinum crucible, and it is mixed that 3g natrium carbonicum calcinatum-borax (mass ratio 2:1) is added
Flux is closed, 1g is covered again after mixing evenly, is then put into platinum crucible in the Muffle furnace for being warming up to 900 DEG C, rise to 1000 DEG C
Melt 30min；
(b) after the platinum crucible of step (a) is slightly cold, the polytetrafluoroethylene beaker of 50mL is removed and placed in from Muffle furnace
In, 25mL ultrapure water, 10mL hydrochloric acid is added, then be put into 200 DEG C of heating plate and extract；
(c) after taking out platinum crucible, 10mL hydrofluoric acid is added, and continues to take out after heating 20min, stands 2 hours；
(d) solution after standing reaction, is filtered by Medium speed filter paper into the plastics volumetric flask of 100mL, constant volume shakes
It is even；
(e) fixed from the plastics volumetric flask for pipetting 10mL to another clean 50mL in the plastics volumetric flask of 100mL
Hold, shake up, as the first solution to be measured；
(f) it by filter residue filtered in step (d) and Medium speed filter paper, moves in high alumina crucible and is gradually warmed up ashing processing
Afterwards, 1g sodium peroxide is added, is stirred evenly, melts 10min at 650 DEG C；
(g) it after taking out by the high alumina crucible in step (f) and is slightly cold, is put into the polytetrafluoroethylene beaker of 50mL, addition
25mL ultrapure water, 10mL hydrochloric acid, after vigorous reaction stopping, low-grade fever high alumina crucible is to extract, then by the solution of extraction
It moves in the Glass capacity bottle of 500mL, constant volume shakes up, as the second solution to be measured；
(h) 6 parts of natrium carbonicum calcinatums-borax (weight ratio 2:1) mixed solvent is weighed, every part of 0.8g to polytetrafluoroethylene (PTFE) is burnt
In cup, add a small amount of water to dissolve, and 5mL hydrochloric acid is added, be transferred in 100mL plastics volumetric flask, then pipette respectively 0mL, 0.5mL,
The lithium of 1.0mL, 1.5mL, 2.0mL, 2.5mL, zirconium, tantalum standard solution into plastics volumetric flask, be configured to 0,5,10,15,20,
The lithium of 25ug/mL, zirconium, tantalum mixed standard solution；ICP-OES test, test successively are carried out to a series of mixed standard solutions
Detection wavelength selects 670.784nm when lithium, and Detection wavelength selects 339.198nm when testing zirconium, and Detection wavelength selects when testing tantalum
240.063nm can obtain the respective standard curve of lithium, zirconium, tantalum respectively；
(i) 6 parts of sodium peroxide solvents are weighed, every part of 0.2g adds a small amount of water to dissolve into polytetrafluoroethylene beaker, and is added
2mL hydrochloric acid is transferred in 100mL Glass capacity bottle, then pipettes the lanthanum standard solution of 0mL, 1mL, 2mL, 3mL, 4mL, 5mL respectively
Into Glass capacity bottle, it is configured to the lanthanum standard solution of 0,10,20,30,40,50ug/mL；Successively to series of standards solution into
Row ICP-OES test, Detection wavelength selects 379.478nm when testing lanthanum, can get the standard curve of lanthanum；
(j) ICP-OES is carried out respectively to step (e) and (g) first solution to be measured obtained respectively and the second solution to be measured
Test, Detection wavelength selects 670.784nm when testing lithium, and Detection wavelength selects 379.478nm when testing lanthanum, detects when testing zirconium
Wavelength selection 339.198nm, Detection wavelength selects 240.063nm when testing tantalum, can get lithium, lanthanum, zirconium, tantalum in filtrate and filter residue
ICP-OES spectral information；
(k) further according to the lithium of step (h) and (i), lanthanum, zirconium, tantalum standard curve, can calculate lithium in filtrate and filter residue,
The respective content of lanthanum, zirconium, tantalum, finally sums up the content in filtrate and filter residue, can be obtained LLZTO solid electrolyte
Li, La, Zr and Ta content in sample.
Wherein, step (h), (i), in (j) using ICP-OES instrument when running parameter it is as shown in table 1.
Table 1
| Running parameter | Numerical value | Running parameter | Numerical value |
| Plasma power/W | 1150 | Right-angle view height/mm | 12 |
| Nebulizer flow/(L/min) | 0.5 | Auxiliary air flow stream/(L/min) | 0.5 |
| Reading number/time | 3 | Analyze pump speed/rpm | 50 |
The calculated result of four kinds of inorganic elements of the embodiment is as shown in table 2, and as can be seen from Table 2, Li, Ta are mainly distributed on
In filtrate, and La is present in substantially in precipitating, and only Zr has a large amount of distribution in filtrate and precipitating, so, it is each inorganic
Content of the element in LLZTO is subject to the total content of filtrate and precipitating.
Table 2
| Element | Wavelength nm | Regression coefficient R2 | Filtrate % | RSD% | Filter residue % | RSD% | Measure total amount w/w% |
| Li | 670.784 | 0.999889 | 5.23 | 0.36 | 0.05 | 1.79 | 5.28 |
| La | 379.478 | 0.999893 | 0.24 | 0.52 | 39.27 | 1.23 | 39.51 |
| Zr | 339.198 | 0.999809 | 7.37 | 0.40 | 4.36 | 0.25 | 11.73 |
| Ta | 240.063 | 0.999946 | 10.99 | 0.68 | 0.12 | 0.68 | 11.11 |
In addition, it is also seen that the test relative standard deviation (RSD) of filtrate and filter residue is both less than 2% from table 2, explanation
The stability of ICP-OES test result is high；Also, the molar ratio of Li, La, Zr, Ta substantially conform to Li7-xLa3Zr2-xTaxO12In
The molar ratio relationship of each inorganic elements, the only slightly biased height of the ratio of Li, this and Li7-xLa3Zr2-xTaxO12It is in preparation process
Make up the vaporization at high temperature of Li and excessive 5~20% related.
In the description of the present invention, it is to be understood that, term " first ", " second " are used for description purposes only, and cannot
It is interpreted as indication or suggestion relative importance or implicitly indicates the quantity of indicated technical characteristic.Define as a result, " the
One ", the feature of " second " can explicitly or implicitly include at least one of the features.In the description of the present invention, " multiple "
It is meant that at least two, such as two, three etc., unless otherwise specifically defined.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (12)
1. a kind of method of inorganic element content in sample for detecting lithium lanthanum zirconium oxygen type solid electrolyte, which is characterized in that described
Inorganic elements includes at least one of lithium, lanthanum and zirconium, which comprises
(1) melting processing is carried out to the sample, add hydrofluoric acid and carries out filtration treatment, to obtain filtrate and filter residue；
(2) alkali fusion processing is carried out to the filter residue, and hydrochloric acid solution is added, to obtain the solution of the filter residue；
(3) using inductive coupling plasma emission spectrograph respectively to the solution of the filtrate and the filter residue, described in progress
The assay of inorganic elements.
2. the method according to claim 1, wherein the lithium lanthanum zirconium oxygen type solid electrolyte is lithium lanthanum zirconium tantalum oxygen
Solid electrolyte, the inorganic elements include at least one of lithium, lanthanum, zirconium and tantalum.
3. method according to claim 1 or 2, which is characterized in that the melting, which is handled, includes:
(1-1) mixes the sample with natrium carbonicum calcinatum, borax, then is warming up under 900~1100 degrees Celsius and melts 15~60
It is cooling after minute；
(1-2) ultrapure water, hydrochloric acid are added into the melt after cooling, extract under 150~250 degrees Celsius.
4. according to the method described in claim 3, it is characterized in that, the sample and the natrium carbonicum calcinatum, the borax
Weight ratio is 3:(60~100): (30~50), and the weight ratio of the natrium carbonicum calcinatum and the borax is 2:1.
5. method according to claim 1 or 2, which is characterized in that the step of addition hydrofluoric acid includes:
The hydrofluoric acid is added to described melt in treated melt in (1-3), the heating reaction 10 under 150~250 degrees Celsius
~30 minutes, and stand and be not less than 0.5 hour.
6. method according to claim 1 or 2, which is characterized in that include: in the step of filtration treatment
(1-4) filtration treatment, to obtain filtrate and filter residue；
The filtrate is moved to constant volume in the volumetric flask of 100mL and forms solution by (1-5)；
(1-6) pipettes the constant volume into the volumetric flask of 50mL of solution described in 10mL, to obtain the first solution to be measured.
7. according to the method described in claim 6, it is characterized in that, alkali fusion processing includes:
(2-1) carries out ashing processing to the filter residue, adds sodium peroxide, and 5~20 are melted under 600~700 degrees Celsius
Minute.
8. the method according to the description of claim 7 is characterized in that the step of addition hydrochloric acid solution, includes:
Ultrapure water, hydrochloric acid is added in the melt of (2-2) Xiang Suoshu alkali fusion processing, is extracted under 150~250 degrees Celsius, it will
The solution of the extraction moves to constant volume in the volumetric flask of 500mL, to obtain the second solution to be measured.
9. according to the method described in claim 8, it is characterized in that, the step of assay of the inorganic elements include:
(3-1) under the corresponding Detection wavelength of the inorganic elements, respectively to the described first solution to be measured and described second to be measured
Solution carries out inductively coupled plasma atomic emission test；
(3-2) calculates the result of the inductively coupled plasma spectrometry test according to the standard curve of the inorganic elements
The sum of the content of the corresponding inorganic elements.
10. according to the method described in claim 9, it is characterized in that,
When the inorganic elements is lithium, the Detection wavelength is 670 ± 1nm；
When the inorganic elements is lanthanum, the Detection wavelength is 379 ± 1nm；
When the inorganic elements is zirconium, the Detection wavelength is 339 ± 1nm；
When the inorganic elements is tantalum, the Detection wavelength is 240 ± 1nm.
11. according to the method described in claim 9, it is characterized in that, the inorganic elements be in lithium, zirconium and tantalum at least
When a kind of, the standard curve of the inorganic elements is that a series of differences are tested by inductive coupling plasma emission spectrograph is dense
What the mixed standard solution of the inorganic elements of degree determined.
12. according to the method described in claim 9, it is characterized in that, the inorganic elements be lanthanum when, the mark of the inorganic elements
Directrix curve is the standard that a series of inorganic elements of various concentrations is tested by inductive coupling plasma emission spectrograph
What solution determined.
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| CN110931847A (en) * | 2019-12-16 | 2020-03-27 | 北京当升材料科技股份有限公司 | Method for treating solid electrolyte and method for testing element content in solid electrolyte |
| CN110931847B (en) * | 2019-12-16 | 2021-03-05 | 北京当升材料科技股份有限公司 | Method for treating solid electrolyte and method for testing element content in solid electrolyte |
| CN114295658A (en) * | 2021-12-10 | 2022-04-08 | 江苏蓝固新能源科技有限公司 | Detection method of solid electrolyte lithium lanthanum zirconium oxygen LLZO material |
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