CN105021576B - The detection method of nonmagnetic metal impurity in cobalt acid lithium or LiMn2O4 - Google Patents
The detection method of nonmagnetic metal impurity in cobalt acid lithium or LiMn2O4 Download PDFInfo
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- CN105021576B CN105021576B CN201510458090.3A CN201510458090A CN105021576B CN 105021576 B CN105021576 B CN 105021576B CN 201510458090 A CN201510458090 A CN 201510458090A CN 105021576 B CN105021576 B CN 105021576B
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 60
- 239000002184 metal Substances 0.000 title claims abstract description 59
- 239000012535 impurity Substances 0.000 title claims abstract description 45
- 239000002253 acid Substances 0.000 title claims abstract description 38
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 32
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 31
- 239000010941 cobalt Substances 0.000 title claims abstract description 31
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 title claims abstract description 30
- 238000001514 detection method Methods 0.000 title claims abstract description 24
- 238000012360 testing method Methods 0.000 claims abstract description 34
- 239000012488 sample solution Substances 0.000 claims abstract description 20
- 239000006228 supernatant Substances 0.000 claims abstract description 18
- 239000000523 sample Substances 0.000 claims description 33
- 230000006641 stabilisation Effects 0.000 claims description 8
- 238000011105 stabilization Methods 0.000 claims description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 26
- 238000004458 analytical method Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 37
- 239000011701 zinc Substances 0.000 description 25
- 239000010949 copper Substances 0.000 description 23
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 23
- 239000007788 liquid Substances 0.000 description 13
- 229910052802 copper Inorganic materials 0.000 description 10
- 229910052725 zinc Inorganic materials 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000005188 flotation Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000011010 flushing procedure Methods 0.000 description 4
- 239000000696 magnetic material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000004088 foaming agent Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008396 flotation agent Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- -1 n-pentyl xanthan Chemical compound 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
Abstract
The invention provides a kind of detection method of nonmagnetic metal impurity in cobalt acid lithium or LiMn2O4, comprise the following steps：1) KCN solution is added into testing sample solution, and the pH value of testing sample solution is maintained at 9.4~9.8；2) supernatant liquor is taken to determine its emissive porwer value；3) content of nonmagnetic metal corresponding to emissive porwer value is read from the standard curve of nonmagnetic metal impurity；Dense >=0.10wt.% of KCN solution in supernatant liquor.Understood by analysis using method provided by the invention, the precision of this method is higher.With preferable reappearance.
Description
Technical field
The present invention relates to chemical field, especially, is related to a kind of inspection of nonmagnetic metal impurity in cobalt acid lithium or LiMn2O4
Survey method.
Background technology
In cobalt acid lithium or the production process of LiMn2O4, it is non magnetic copper, zinc or nickel etc. to be mixed into products therefrom unavoidably
Metal impurities.The presence of metal impurities is to cobalt acid lithium or LiMn2O4 as battery material in use, causing many adverse effects.Example
Gained battery short circuit, battery performance can such as declined.And there is no magnetic for these metal impurities, it is difficult to pass through the magnetic of routine
Choosing method makes it be separated with cobalt acid lithium or LiMn2O4.
To contained nonmagnetic metal foreign matter in cobalt acid lithium or LiMn2O4, detected more using flotation partition method.Including with
Lower step：1) 500g samples are weighed, add 1500ml deionized water and flotation agent thereto, have been stirred on flotation device certain
Foaming agent is added after time, controls gas flow, foam is collected, Cu is flotated, filter residue is stayed after suction filtration.2) then proceed to
With flotation Zn in a sample, flotation Zn process will add NaOH and CuSO4Auxiliary, timing is stirred, put into foaming agent, collected
Foam, it is repeated twice, after Zn flotation is complete, suction filtration stays filter residue.3) mixed liquor of hydrogen peroxide and ammoniacal liquor is added in filter residue, carries out the
Secondary suction filtration, reserved filtrate, heating adds concentrated nitric acid after 30 minutes and neutralized, molten using this by solution constant volume after reheating 20 minutes
Liquid measures Cu and Zn contained therein amount respectively.The method operating process is complicated, and agents useful for same includes flotation agent (n-pentyl xanthan
Sour potassium), foaming agent, sodium hydroxide, copper sulphate, ammoniacal liquor (dense), hydrogen peroxide (dense), nitric acid (dense), acetate fiber filter membrane and PP filter
Film, and agents useful for same is both needed to for extra-pure grade, cause testing cost higher.And need three people same during whole separation detection
When operate, and be only capable of the sample of 7 batches of single treatment, expend larger manpower and materials.Because detection process complex steps are numerous
It is more, caused accidental error in either step, the stability of final detection result can be affected greatly.
The nonmagnetic metal being present in cobalt acid lithium or LiMn2O4 is different from the form being present in mineral, causes detecting
During, testing result is highly prone to the interference of cobalt acid lithium or LiMn2O4.It is thus conventional to be used for various metallic elements in mineral
The method of content detection can not be suitable for handling the material based on cobalt acid lithium or LiMn2O4.
The content of the invention
The present invention provides a kind of detection method of nonmagnetic metal impurity in cobalt acid lithium or LiMn2O4, to solve existing detection
The technical problem that method cost is high, efficiency is low and cumbersome.
The invention provides a kind of detection method of contained nonmagnetic metal impurity in cobalt acid lithium or LiMn2O4, including it is following
Step：1) KCN solution is added into testing sample solution, and the pH value of testing sample solution is maintained at 9.4~9.8；2) take
Its luminous intensity is determined after supernatant liquor acidifying；3) it is corresponding that emissive porwer value is read from the standard curve of nonmagnetic metal impurity
Nonmagnetic metal content；Concentration >=0.10wt.% of KCN solution in supernatant liquor.
Further, pH value 9.4.
Further, sample emission intensity value is measured by ICP instrument.
Further, the wavelength selected by ICP instrument measure Cu contents is appointed for 224.700nm, 324.754nm or 213.598nm
One；Wavelength selected by ICP instrument measure Zn contents is that 202.54nm, 213.85nm or 206.200nm are any.
Further, condition determination to rinse 45~55rpm of pump speed, analyzes pump speed 45~55rpm, RF power in ICP instrument
1100~1200w, pump stabilization time 5s, secondary air amount 0.1~0.8L/ minutes.
Further, it is additionally included in the testing sample solution in step 1) and adds for removing magnetic in testing sample solution
The magnet of property metal impurities.
The invention has the advantages that：
Method provided by the invention is controlled and is somebody's turn to do by adding potassium cyanide solution into cobalt acid lithium or LiMn2O4 sample solution
The pH value of solution so that the nonmagnetic metal only in sample dissolves, and any dissolving does not occur for cobalt acid lithium or LiMn2O4.From
And it can accurately detect contained nonmagnetic metal impurity in cobalt acid lithium or LiMn2O4 sample by determining the emissive porwer value of solution
Content.Understood by analysis using method provided by the invention, the precision of this method is higher.With preferable reappearance.
In addition to objects, features and advantages described above, the present invention also has other objects, features and advantages.
Below with reference to figure, the present invention is further detailed explanation.
Brief description of the drawings
The accompanying drawing for forming the part of the application is used for providing a further understanding of the present invention, schematic reality of the invention
Apply example and its illustrate to be used to explain the present invention, do not form inappropriate limitation of the present invention.In the accompanying drawings：
Fig. 1 is the process flow diagram of the preferred embodiment of the present invention.
Embodiment
Embodiments of the invention are described in detail below in conjunction with accompanying drawing, but the present invention can be defined by the claims
Implement with the multitude of different ways of covering.
Unless otherwise specified, the conventional meanses that technological means used in embodiment is well known to those skilled in the art.
The percentage sign " % " being referred to herein, if not specified, refers to mass percent；But the percentage of solution,
Unless otherwise specified, refer to contain some grams of solute in solution 100m1；Percentage between liquid, refer to the capacity at 20 DEG C
Ratio.Nonmagnetic metal herein refers to the metal without magnetic during without magnetization treatment.
Because the content of thing to be detected in measured sample is too low, therefore need to be measured using ICP instrument, could be by determinand
Content measurement come out.ICP instrument can be other ICP instrument such as ICP-AES or ICP-MS.
The invention provides a kind of detection method of contained nonmagnetic metal impurity in cobalt acid lithium or LiMn2O4, including it is following
Step：After magnetic metal impurity in testing sample solution is removed, KCN solution is added into testing sample solution, and make to be measured
The pH value of sample solution is maintained at 9.4~9.8；Supernatant liquor is taken to determine its emissive porwer value afterwards；From nonmagnetic metal impurity
Standard curve in read emissive porwer value corresponding to nonmagnetic metal content.Method provided by the invention is by treating test sample
KCN solution is added in the aqueous solution of product, and keeps the pH value of testing sample solution to be maintained at 9~10.On this condition, guarantor can be seen
Nonmagnetic metal in card sample is sufficiently dissolved, while avoids the materials such as cobalt acid lithium or LiMn2O4 from occurring in the process
Dissolving.Basis is provided to obtain accurate namagnetic substance content during subsequent detection.After detected sample forms solution,
LiMn2O4 or cobalt acid lithium can interfere to the dissolving of micro nonmagnetic metal contained therein.So that there is error in testing result.
By adding KCN in the solution and keeping the pH value of solution effectively to prevent LiMn2O4 or cobalt acid lithium to non magnetic for 9.4~9.8
Harmful effect caused by the dissolving of metal.So as to improve measurement result.
Magnetic metal impurity in handled testing sample solution can be stirred by adding the materials such as magnet in the solution
After mixing a period of time, magnetisable material is removed.So as to prevent interference of the magnetic metal impurity to testing result.
Testing sample solution can be the aqueous solution can also be other will not make LiMn2O4 or cobalt acid lithium dissolve it is molten
Agent.To promote the dissolving of nonmagnetic metal impurity, by stirring sample can be made to be dispersed in solution, and fully and KCN
Contact.Realize dissolving.
Concentration >=0.1wt.% of KCN solution in supernatant liquor.Now KCN solvability can be only limitted to non magnetic
The dissolving of metal impurities, avoid producing dissolving to other particles, so as to cause the deviation of testing result.KCN is added in this ratio
It can prevent KCN from producing dissolving to other materials, so as to interference detection results.So that testing result is optimal.
Preferably, the concentration for adding KCN solution is 7%.LiMn2O4 or cobalt acid can be avoided completely by adding the KCN of the concentration
The dissolution of lithium, while the result of extraction of nonmagnetic metal impurity is reached excellent, so that testing result reaches most accurate.
Preferably, pH value 9.4.On this condition, the solubility of the nonmagnetic metal in sample is optimal, while again
It is avoided that when using KCN, dissolving advantage can not be occupied in system because pH value is unfavorable for KCN, it is non-in sample so as to have impact on
The solute effect of magnetic metal.Enable nonmagnetic metal material and KCN it is fully oxidized-complexing, well into solution, improve
The accuracy of testing result.In order to keep the stability of the pH value of solution, prevent from that big ups and downs occur in use, so as to
Influence the solution modeling of nonmagnetic metal in sample.It is preferred that solution ph buffer solvent is additionally added in solution.Preferably ammonium chloride.
Nonmagnetic metal impurity dissolving in treated testing sample enters in clear liquid, after stirring is stood, makes
Obtaining nonmagnetic metal impurity can fully dissolve, and avoid the situation of missing inspection from occurring.Afterwards after stratification, supernatant liquor is taken.Clear liquid
In contain most of nonmagnetic metal impurity in sample., can be according to instrument to filtrate before emissive porwer value is determined
Handled.
The content of contained nonmagnetic metal impurity is relatively low in sample, only ppb levels, therefore the minimum detection of detecting instrument used
Limit must reach 0.0009 μ g/ml.Emissive porwer value measures preferably through ICP instrument (plasma spectrometer).Equipment spirit
Sensitivity and the degree of accuracy are higher.So as to ensure that the accuracy to the detection result of micro nonmagnetic metal impurity in sample.
When being detected using ICP instrument, solution, which needs first to be acidified, to be used.Acidifying can be carried out according to a conventional method.Such as can be in filtrate
Middle addition 1+1 hydrochloric acid and 1+1 nitric acid, the pH value of filtrate is set to be less than 7.
When using ICP instrument, the impurity that solution is dissolved in order to avoid other interferes to testing result, preferably ICP
Wavelength selected by instrument measure Cu contents is that 224.700nm, 324.754nm or 213.598nm are any；Selected by ICP instrument measure Zn contents
Wavelength is that 202.54nm, 213.85nm or 206.200nm are any.Detected by this wavelength, other in solution can be avoided
The interference of impurity both main nonmagnetic metal defects inspecting results to Cu and Zn, improve the accuracy of testing result.
Preferably, condition determination to rinse 45~55rpm of pump speed, analyzes pump speed 45~55rpm, RF power in ICP instrument
1100~1200w, pump stabilization time 5s, secondary air amount 0.1~0.8L/ minutes.Detected, can be improved on this condition
The accuracy of acquired results.Prevent the influence of other metal impurities, LiMn2O4 or cobalt acid lithium to testing result in solution.More preferably
To rinse pump speed 50rpm, analysis pump speed 50rpm, RF power 1150w, pump stabilization time 5s, secondary air amount 0.5L/ minutes, hang down
Straight observed altitude 12.0mm.Testing result accuracy obtains optimal on this condition.
After the emissive porwer value for determining solution, on the standard curve of emissive porwer value-concentration, corresponding lookup draws the hair
Penetrate the solution concentration i.e. content of nonmagnetic metal corresponding to intensity level.Such as when the nonmagnetic metal that need to be detected is Cu and Zn,
Cu, Zn can be prepared and mix the standard liquid that target concentration is followed successively by 0,20ppb, 50ppb, 100ppb, 200ppb, medium is 5% nitre
Acid.Emissive porwer value is drawn by ICP instrument measure under the same conditions, and draws normal concentration-emissive porwer value curve.
Referring to Fig. 1, when method provided by the invention is used for ICP instrument, comprise the following steps：
S1：Dissolve nonmagnetic metal impurity：Concentration is added in testing sample solution and is 6% KCN, and keeps solution
PH value is 9.4, and stirring adds NH4Cl solid powder 0.6g, magnet is added, two pairs of rollers stir 2 hours, take out magnet and (are used to determine
Magnetic Materials), half an hour is stood, pours out supernatant liquor, set aside for use.
S2：Stand：After standing a period of time, undissolved material is removed, obtains supernatant liquor；
S3：Acid adjustment：The pH value of supernatant liquor is adjusted to less than 7.The various acid that will not be interfered to detection can be used.
S4:Emissive porwer value compares：Solution after acid adjustment is put into ICP instrument and determines its emissive porwer value, and in standard
Tenor corresponding to specific emissive porwer value is searched in curve, so as to draw the numerical value.
This method is it is possible to prevente effectively from existing method, it is necessary to the processing method of flotation repeatedly is carried out to sample, is avoiding manganese
In the case that sour lithium or cobalt acid lithium dissolve, the dissolving of other impurities is controlled, so as to ensure that nonmagnetic metal impurity content
The accuracy of measurement result.
Embodiment
Instrument and reagent are commercially available in following examples and comparative example.
Cu or Zn standard curve determination methods：
A) standard liquid that Cu or Zn concentration is followed successively by 0,20ppb, 50ppb, 100ppb, 200ppb, dissolving medium are prepared
For 5% nitric acid；
B) standard liquid is measured to the emissive porwer value of each standard liquid on ICP instrument respectively, measuring condition is flushing
Pump speed 50rpm, analyze pump speed 50rpm, RF power 1150w, pump stabilization time 5s, secondary air amount 0.5L/min, Vertical Observation
Height 12.0mm.Wavelength when measuring Cu standard liquids is 213.59nm；Wavelength when measuring Zn standard liquids is 206.200nm
C) using Cu or Zn concentration as abscissa, measured emissive porwer value is ordinate, and drafting obtains Cu or Zn standard
Curve.
Specimen in use is with a sample, wherein Cu contents and Zn content all sames in embodiment 1~4.
Embodiment 1
A, 450g samples are placed in the measure special bottle of magnetic metal simple substance, it is accurate to add 350ml water, and add
5wt.% KCN solution, NH4Cl solid powder 0.6g, magnet is added, and keep the pH most 9.4 of solution to be measured.Two pairs of rollers stir
2 hours, magnet (being used to determine Magnetic Materials) is taken out, half an hour is stood, pours out supernatant liquor in clean 250ml beakers.It is quiet
Put stand-by, supernatant KCN content is 0.1wt.%.
B, the clear liquid for taking 50ml steps 1 to collect accurately is divided to be boiled in acid in the 250ml beakers cleaned with 50ml pipettes,
Duplicate Samples are pipetted, add 9ml (1+1) HCl, 3ml (1+1) HNO3, concentrating sample is heated to below 5ml, is carefully transferred to sample
In 10ml color-comparison tubes, constant volume shakes up.
C, ICP is tested, and condition is flushing pump speed 50rpm, analyzes pump speed 50rpm, RF power 1150w, pump stabilization time 5s,
Secondary air amount 0.5L/min, Vertical Observation height 12.0mm.
Wavelength Cu during measurement：213.598nm.Zn：206.200nm.Contained Cu contents in sample are read on standard curve
With Zn contents.
Embodiment 2
A, 550g samples are placed in the measure special bottle of magnetic metal simple substance, add 350ml distilled water, obtain treating test sample
Product solution, KCN solution is added, add NH4Cl solid powder 0.6g, magnet is added, the pH value of solution to be detected is 9.5.Two pairs of rollers
Stirring 2 hours, magnet (being used to determine Magnetic Materials) is taken out, half an hour is stood, pours out supernatant liquor in clean 250ml beakers
In.Set aside for use.The content of KCN in supernatant liquor is 0.11wt.%.
B, the clear liquid for taking 50ml steps 1 to collect accurately is divided to be boiled in acid in the 250ml beakers cleaned with 50ml pipettes,
Duplicate Samples are pipetted, add 9ml (1+1) HCl, 3ml (1+1) HNO3, concentrating sample is heated to below 5ml, is carefully transferred to sample
In 10ml color-comparison tubes, constant volume shakes up.
C, ICP is tested, and condition is flushing pump speed 55rpm, analyzes pump speed 55rpm, RF power 1200w, pump stabilization time 5s,
Secondary air amount 0.8L/ minutes.Vertical Observation height 12.0mm.
Wavelength Cu during measurement：224.700nm.Zn：202.548nm.Contained Cu contents in sample are read on standard curve
With Zn contents.
Embodiment 3
A, 350g samples are placed in the measure special bottle of magnetic metal simple substance, add 350ml deionized waters, obtain to be measured
Sample solution, KCN solution is added, add NH4Cl solid powder 0.6g, magnet is added, the pH value of solution to be detected is 9.8.It is right
Roller stirs 2 hours, takes out magnet (being used to determine Magnetic Materials), stands half an hour, pour out supernatant liquor in clean 250ml beakers
In.Set aside for use.The content of KCN in supernatant liquor is 0.12wt.%.
B, the clear liquid for taking 50ml steps 1 to collect accurately is divided to be boiled in acid in the 250ml beakers cleaned with 50ml pipettes,
Duplicate Samples are pipetted, add 9ml (1+1) HCl, 3ml (1+1) HNO3, concentrating sample is heated to below 5ml, is carefully transferred to sample
In 10ml color-comparison tubes, constant volume shakes up.
C, ICP is tested, and condition is flushing pump speed 45rpm, analyzes pump speed 45rpm, RF power 1100w, pump stabilization time 5s,
Secondary air amount 0.1L/ minutes.Vertical Observation height 12.0mm.
Wavelength Cu during measurement：324.754nm.Zn：213.856nm.Contained Cu contents in sample are read on standard curve
With Zn contents.
Embodiment 4
Difference with embodiment 1 is：The emissive porwer value of sample solution is measured by ICP-AES.
The method of embodiment 1~4 is repeated 8 times, respectively the Cu contents and Zn contents in determination sample.To 8 measurement results
Statistical disposition is carried out, the precision of the present invention is assessed according to relative standard deviation (RSD).Analysis result is listed in Tables 1 and 2.
The embodiment 1~4 of table 1 detects Cu content Precision Analyze table (units：ppb)
| Test number (TN) | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | Average value | Standard deviation | RSD (%) |
| Embodiment 1 | 13.8 | 13.2 | 13.2 | 14.0 | 13.5 | 14.1 | 13.5 | 13.7 | 13.6 | 0.34 | 2.47 |
| Embodiment 2 | 11.6 | 10.9 | 11.5 | 11.5 | 10.9 | 10.7 | 10.8 | 10.9 | 11.1 | 0.37 | 3.30 |
| Embodiment 3 | 34.4 | 34.3 | 33.9 | 34.5 | 33.9 | 33.5 | 34.5 | 33.8 | 34.1 | 0.37 | 1.10 |
| Embodiment 4 | 23.7 | 23.5 | 24.0 | 23.9 | 24.5 | 23.5 | 23.6 | 23.5 | 23.8 | 0.35 | 1.47 |
The embodiment 1~4 of table 2 detects Zn content Precision Analyze table (units：ppb)
| Test number (TN) | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | Average value | Standard deviation | RSD (%) |
| Embodiment 1 | 12.0 | 11.1 | 12.1 | 11.9 | 11.3 | 11.4 | 11.5 | 11.9 | 11.7 | 0.37 | 3.18 |
| Embodiment 2 | 20.8 | 20.5 | 20.3 | 20.6 | 21.0 | 20.5 | 20.8 | 20.9 | 20.7 | 0.24 | 1.15 |
| Embodiment 3 | 6.5 | 6.5 | 6.8 | 6.5 | 6.8 | 6.4 | 6.3 | 6.8 | 6.6 | 0.20 | 3.01 |
| Embodiment 4 | 18.9 | 19.5 | 19.3 | 19.0 | 18.9 | 19.2 | 19.3 | 19.2 | 19.2 | 0.21 | 1.11 |
From table 1~2, after method provided by the invention is repeated 8 times, for Cu and Zn content detection result (unit
For ppb) RSD far smaller than 5.0%, illustrate that method provided by the invention has preferable precision, can accurate measurement sample
In contained nonmagnetic metal content.And it is simple to operate, as a result accurately.Suitable for industrialized production.
It is less than 0.5% impurity generally for content in sample, the relative standard deviation (RSD) of peak area should be less than
10%；Impurity of the content 0.5%~2%, the RSD of peak area should be less than 5%；Content is more than 2% impurity, peak area
RSD should be less than 2%.Thus method provided by the invention for the relatively low material of impurity content above-mentioned testing result, far
Requirement and standard far above prior art.Illustrate this method favorable reproducibility, accuracy height.It is adapted to detection cobalt acid lithium or LiMn2O4
In contained nonmagnetic metal impurity.
The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.Within the spirit and principles of the invention, that is made any repaiies
Change, equivalent substitution, improvement etc., should be included in the scope of the protection.
Claims (6)
1. the detection method of nonmagnetic metal impurity in a kind of cobalt acid lithium or LiMn2O4, it is characterised in that comprise the following steps：
1) KCN solution is added into testing sample solution, and the pH value of the testing sample solution is maintained at 9.4~9.8；
2) supernatant liquor is taken to determine its emissive porwer value after being acidified；
3) containing for nonmagnetic metal corresponding to the emissive porwer value is read from the standard curve of the nonmagnetic metal impurity
Amount；
Concentration >=0.10wt.% of KCN solution in the supernatant liquor.
2. the detection method of nonmagnetic metal impurity in cobalt acid lithium according to claim 1 or LiMn2O4, it is characterised in that
The pH value is 9.4.
3. the detection method of nonmagnetic metal impurity in cobalt acid lithium according to claim 1 or LiMn2O4, it is characterised in that
The sample emission intensity value is measured by ICP instrument.
4. the detection method of nonmagnetic metal impurity in cobalt acid lithium according to claim 3 or LiMn2O4, it is characterised in that
Wavelength selected by the ICP instrument measure Cu contents is that 224.700nm, 324.754nm or 213.598nm are any；The ICP instrument measure
Wavelength selected by Zn contents is that 202.54nm, 213.85nm or 206.200nm are any.
5. the detection method of nonmagnetic metal impurity in cobalt acid lithium according to claim 4 or LiMn2O4, it is characterised in that
Condition determination analyzes pump speed 45~55rpm, RF 1100~1200w of power, pump to rinse 45~55rpm of pump speed in the ICP instrument
Stabilization time 5s, secondary air amount 0.1~0.8L/ minutes.
6. the detection method of nonmagnetic metal impurity in cobalt acid lithium according to claim 1 or LiMn2O4, it is characterised in that
It is additionally included in the testing sample solution in the step 1) and adds for removing magnetic gold in the testing sample solution
Belong to the magnet of impurity.
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| CN101464443A (en) * | 2007-12-21 | 2009-06-24 | 深圳市比克电池有限公司 | Method for measuring anode slurry equality |
| CN103728228A (en) * | 2012-10-10 | 2014-04-16 | 三星Sdi株式会社 | Method for detecting non-magnetic metal particles contained in secondary battery materials |
| CN103972479A (en) * | 2014-05-27 | 2014-08-06 | 中国科学院宁波材料技术与工程研究所 | Ion battery |
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| CN101464443A (en) * | 2007-12-21 | 2009-06-24 | 深圳市比克电池有限公司 | Method for measuring anode slurry equality |
| CN103728228A (en) * | 2012-10-10 | 2014-04-16 | 三星Sdi株式会社 | Method for detecting non-magnetic metal particles contained in secondary battery materials |
| CN103972479A (en) * | 2014-05-27 | 2014-08-06 | 中国科学院宁波材料技术与工程研究所 | Ion battery |
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