CN105842266A - Fluorescence analysis method for determining element content in lithium iron phosphate - Google Patents
Fluorescence analysis method for determining element content in lithium iron phosphate Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 32
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 13
- 238000012921 fluorescence analysis Methods 0.000 title claims abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 49
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000004846 x-ray emission Methods 0.000 claims abstract description 38
- 239000012086 standard solution Substances 0.000 claims abstract description 21
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000003825 pressing Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000000523 sample Substances 0.000 claims description 67
- 239000000243 solution Substances 0.000 claims description 61
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 45
- 238000012360 testing method Methods 0.000 claims description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- 239000001117 sulphuric acid Substances 0.000 claims description 11
- 235000011149 sulphuric acid Nutrition 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- -1 diphenylamine sulfonic acid sodium salt Chemical class 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 239000012488 sample solution Substances 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 239000011609 ammonium molybdate Substances 0.000 claims description 8
- 229940010552 ammonium molybdate Drugs 0.000 claims description 8
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 7
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 7
- 239000001119 stannous chloride Substances 0.000 claims description 7
- 235000011150 stannous chloride Nutrition 0.000 claims description 7
- 229910010062 TiCl3 Inorganic materials 0.000 claims description 6
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- JXDYKVIHCLTXOP-UHFFFAOYSA-N isatin Chemical compound C1=CC=C2C(=O)C(=O)NC2=C1 JXDYKVIHCLTXOP-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 5
- 244000061458 Solanum melongena Species 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- HYKDWGUFDOYDGV-UHFFFAOYSA-N 4-anilinobenzenesulfonic acid Chemical compound C1=CC(S(=O)(=O)O)=CC=C1NC1=CC=CC=C1 HYKDWGUFDOYDGV-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 238000000247 postprecipitation Methods 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- QLULGSLAHXLKSR-UHFFFAOYSA-N azane;phosphane Chemical compound N.P QLULGSLAHXLKSR-UHFFFAOYSA-N 0.000 claims description 2
- XMXNVYPJWBTAHN-UHFFFAOYSA-N potassium chromate Chemical compound [K+].[K+].[O-][Cr]([O-])(=O)=O XMXNVYPJWBTAHN-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 10
- 239000011574 phosphorus Substances 0.000 abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 9
- 229910052742 iron Inorganic materials 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- YVBOZGOAVJZITM-UHFFFAOYSA-P ammonium phosphomolybdate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])=O.[O-][Mo]([O-])(=O)=O YVBOZGOAVJZITM-UHFFFAOYSA-P 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000007704 wet chemistry method Methods 0.000 description 5
- 239000010405 anode material Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000003556 assay Methods 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 238000005056 compaction Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000010959 commercial synthesis reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000012445 acidic reagent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- AMWVZPDSWLOFKA-UHFFFAOYSA-N phosphanylidynemolybdenum Chemical compound [Mo]#P AMWVZPDSWLOFKA-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000012096 transfection reagent Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/223—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material by irradiating the sample with X-rays or gamma-rays and by measuring X-ray fluorescence
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2223/00—Investigating materials by wave or particle radiation
- G01N2223/07—Investigating materials by wave or particle radiation secondary emission
- G01N2223/076—X-ray fluorescence
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Analysing Materials By The Use Of Radiation (AREA)
Abstract
The invention discloses a fluorescence analysis method for determining the content of a ferrophosphorus element in lithium iron phosphate, which comprises equally dividing a lithium iron phosphate sample into three parts; treating a first lithium iron phosphate sample by using hydrochloric acid, filtering, and titrating by using a potassium dichromate standard solution to obtain the content of iron element; treating a second lithium iron phosphate sample by using hydrochloric acid, filtering, and measuring the content of phosphorus by using an ammonium phosphomolybdate volumetric method; preparing a third lithium iron phosphate sample into six standard samples with different contents; respectively pressing the materials into sheets, and measuring the fluorescence intensity of iron and phosphorus elements in each sheet standard sample by an X-ray fluorescence spectrometry; plotting an XRF standard curve; pressing a lithium iron phosphate sample to be detected into a sheet shape, and measuring the fluorescence intensity of the sheet shape; and obtaining the contents of iron and phosphorus elements through an XRF standard curve. The method combining the wet chemical method and the X-ray fluorescence spectrometry is fast and high-speed, and has the advantages of simple operation, small error, long consumption time and environmental pollution.
Description
Technical field
The present invention relates to technical field of lithium ion, be specifically related to one and utilize X-ray fluorescence spectra assay
The method of ferrum, phosphorus element content in lithium cell anode material of lithium iron phosphate.
Background technology
LiFePO4 is the phosphate of a kind of olivine structural, its Stability Analysis of Structures, is that current lithium ion battery is conventional just
One of pole material.At present, the LiFePO4 of commercial synthesis is possibly together with a small amount of impurity component, therefore as a kind of lithium ion battery just
Pole material, the content of its essential element ferrum element and P elements is the key index of its criterion of acceptability.
And current, method many employings " GB/T30835-of lithium ion battery industrial test ferrum element and phosphorus element content
2014 lithium ion batteries charcoal composite lithium iron phosphate cathode material ".The method is wet chemistry method, complex operation, and operating error is big,
Elapsed time is long, and reagent type is many；And the environmental pollution such as required reagent potassium dichromate is the most heavier.Therefore, exploitation is a kind of quickly
And the method for green detects constituent content tool in LiFePO4 and is of great significance.
X-ray fluorescence spectroscopy (XRF) is a kind of to analyze that speed is fast, sample preparation is simple, it is not necessary to using poisonous has pollution
Reagent, it is not required that the method for time-consuming pretreatment process, can be used to test containing of ferrum element and P elements in LiFePO4
Amount, the method relies on the standard curve that in standard sample, the fluorescence intensity of element is set up with content.At present, XRF is used for building
The analysis of the field samples such as material, pottery, metal material.For now, the iron phosphate lithium positive pole in lithium ion battery industry
Ferrum element and the content of P elements in material there is no the report using XRF quickly to measure.
Summary of the invention
It is an object of the invention to provide a kind of easy to operate, sample preparation is simple, detection process need not poisonous have dirt
The method of transfection reagent detects ferrum element and the content of P elements in the LiFePO4 of commercial synthesis.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of for measuring the fluorescence analysis method of ferrophosphorus constituent content in LiFePO4, comprise the following steps:
(1) take with a batch of LiFePO4 sample, and be bisected into three parts；
(2) use first part of LiFePO4 sample of HCl treatment, after filtering unreacted carbon, form testing sample solution；With weight
It is titrated by Neutral potassium chromate standard solution, records the content of ferrum element in testing sample solution；
(3) use second part of LiFePO4 sample of HCl treatment, after filtering unreacted carbon, form testing sample solution；Use phosphorus
Ammonium molybdate volumetric method records the content of P elements in testing sample solution；
(4) the 3rd part of LiFePO4 sample is divided at least six parts, is separately added into the calcium carbonate primary standard substance of different content, joins
Make the standard sample that content is different；Use powder pressing method to be compressed into tablet form respectively by each standard sample again, then pass through X
Ray fluorescence spectrometry records ferrum, the fluorescence intensity of P elements in each lamellar standard sample；
(5) by strong by the fluorescence of ferrum in the LiFePO4 sample measured by X-ray fluorescence spectroscopy, P elements in step (4)
Degree, is associated with by ferrum, the content of P elements in the LiFePO4 sample measured by step (2), (3), is formed with fluorescence
Intensity is vertical coordinate, with ferrum, the content XRF standard curve as abscissa of P elements；
(6) use the powder pressing method identical with step (4) to be compressed into tablet form by LiFePO4 sample to be measured, obtain to be measured
Sample, records the fluorescence intensity of each element in testing sample by X-ray fluorescence spectroscopy；Marked by the XRF of step (5) gained
Directrix curve, can draw the content of ferrum in testing sample, P elements.
Scheme further, in described step (2), adds first part of LiFePO4 sample in hydrochloric acid solution, heated and boiled
And keep 18-25min, and it being then cooled to room temperature, and filter out unreacted carbon, the solution after filtration is with stannous chloride solution also
Former ferric iron therein, is subsequently adding indicator, forms solution to be measured.
Further scheme, described aqueous hydrochloric acid solution refers to that concentrated hydrochloric acid that mass concentration is 36% and one-level water are according to quality
Than carry out mixing for 1:1；
Described stannous chloride solution refers to be dissolved in hydrochloric acid stannum dichloride, then to be diluted with water to concentration be 50g/L；
Described indicator is CuSO4-isatin indicator, diphenylamine sulfonic acid sodium salt indicator；Add CuSO4-isatin indicator is by light
Yellow solution becomes green, then drips TiCl3After solution disappears to green, excess half, after placement, solution becomes blue；Add again
After entering sulphuric acid/phosphoric acid mixing acid and diphenylamine sulfonic acid sodium salt indicator, form solution to be measured.
Preferred version, described CuSO4-isatin indicator refers to that isatin is dissolved in aqueous sulfuric acid, and then constant volume is to sulfur
In acid copper solution；
Described TiCl3Solution refers to the titanous chloride. hydrochloric acid solution that concentration is 20g/L；
Described sulphuric acid/phosphoric acid mixing acid is the concentrated sulphuric acid of employing 95 ~ 98wt% and the phosphoric acid of 85wt% is that 1:1 mixes according to volume ratio
Close, be diluted to 1L with one-level water the most again and be made into 15wt %；
Described diphenylamine sulfonic acid sodium salt indicator refers to the diphenylamine sulfonic acid sodium water solution that concentration is 0.05g/ L.
Scheme, titrates with potassium dichromate standard solution in described step (2), when solution is transformed into by blueness further
Aubergine is reaction end.
Scheme, in described step (3), filters the solution ammonia after unreacted carbon and has been neutralized to hydroxide further
Precipitation occurs, then precipitates with hydroxide with in nitric acid standard solution, and makes it just disappear；It is subsequently adding excess nitric acid standard
Solution, is slowly added to ammonium molybdate solution, and vibrate 2 ~ 3min postprecipitation, and places more than 4h, obtains the content of wherein P elements.
The method that the present invention combines first with wet chemistry method and X fluorescence spectrum method, draw with fluorescence intensity as vertical coordinate,
With ferrum, the content XRF standard curve as abscissa of P elements, then using this XRF standard curve as standard, and penetrated by X
Line fluorescent spectrometry records the fluorescence intensity of each element in testing sample, detects phosphorus in LiFePO4 the most to be measured, ferrum unit
The content of element.The quick high speed of detection method, and simple to operate, error is little, elapsed time is long, environmental pollution environmental protection.
Beneficial effects of the present invention is as follows:
(1) present invention uses the mode that wet chemistry method and X fluorescence spectrum method combine, thus in rapid and accurate determination LiFePO4
Ferrum element and the content of P elements；
(2) present invention is by the content of the various elements in wet chemistry method definite value inspection LiFePO4 sample, and based on this
Making XRF standard sample, recycling XRF obtains corresponding standard curve, efficiently solves the XRF standard in LiFePO4 sample
A curve plotting difficult problem；
(3) present invention uses XRF standard curve, and measures ferrum element and P elements in LiFePO4 by X fluorescence spectrum method
Content, thus decrease the use of toxic chemical, reduce cost, and improve the testing time, it is a kind of environmental protection
Method of testing.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in detail.
In following example, hydrochloric acid, sulphuric acid, phosphoric acid are on market the undiluted reagent sold.
Wherein selected aqueous hydrochloric acid solution refers to that the concentrated hydrochloric acid that mass concentration is 36% is 1 with one-level water according to mass ratio:
1 carries out mixing；
Described stannous chloride solution refers to be dissolved in hydrochloric acid stannum dichloride, then to be diluted with water to concentration be 50g/L；
Described CuSO4-isatin indicator refers to that isatin is dissolved in aqueous sulfuric acid, and then constant volume is in copper-bath；
Described TiCl3Solution refers to the titanous chloride. hydrochloric acid solution that concentration is 20g/L；
Described sulphuric acid/phosphoric acid mixing acid is the concentrated sulphuric acid of employing 95 ~ 98wt% and the phosphoric acid of 85wt% is that 1:1 mixes according to volume ratio
Close, be diluted to 1L with one-level water the most again and be made into 15wt %；
Described diphenylamine sulfonic acid sodium salt indicator refers to the diphenylamine sulfonic acid sodium water solution that concentration is 0.05g/ L.
Embodiment 1
A kind of for measuring the fluorescence analysis method of ferrophosphorus constituent content in LiFePO4, comprise the following steps:
(1) take with a batch of LiFePO4 sample, and be bisected into three parts；
(2) being added in aqueous hydrochloric acid solution by first part of LiFePO4 sample, heated and boiled also keeps 18-25min, is subsequently cooled to
Room temperature, and filter out unreacted carbon, the solution stannous chloride solution reduction ferric iron therein after filtration, it is subsequently adding
CuSO4Yellow solution is become green by-isatin indicator, then drips TiCl3After solution disappears to green, excess half, place
Rear solution becomes blue；After adding sulphuric acid/phosphoric acid mixing acid and diphenylamine sulfonic acid sodium salt indicator, form solution to be measured；With weight chromium
It is titrated by acid potassium standard solution, is reaction end when solution is transformed into aubergine by blueness, i.e. records testing sample
The content of ferrum element in solution；
(3) use second part of LiFePO4 sample of HCl treatment, after filtering unreacted carbon, be neutralized to hydroxide with ammonia
Precipitation occurs, then precipitates with hydroxide with in nitric acid standard solution, and makes it just disappear；It is subsequently adding excess nitric acid standard
Solution, is slowly added to ammonium molybdate solution, and vibrate 2 ~ 3min postprecipitation, and places 4h testing sample solution formed above；I.e. record
The content of P elements in testing sample solution；
(4) the 3rd part of LiFePO4 sample is divided at least six parts, is separately added into the calcium carbonate primary standard substance of different content, joins
Make the standard sample that content is different；Use powder pressing method to be compressed into tablet form respectively by each standard sample again, then pass through X
Ray fluorescence spectrometry records ferrum, the fluorescence intensity of P elements in each lamellar standard sample；
(5) by miscellaneous by ferrum, P elements and metal in the LiFePO4 sample measured by X-ray fluorescence spectroscopy in step (4)
The fluorescence intensity of prime element, closes with by ferrum, the content of P elements in the LiFePO4 sample measured by step (2), (3)
Connection, forms the XRF standard curve with fluorescence intensity as vertical coordinate, with the content of ferrum P elements as abscissa；
(6) use the powder pressing method identical with step (4) to be compressed into tablet form by LiFePO4 sample to be measured, obtain to be measured
Sample, records the fluorescence intensity of each element in testing sample by X-ray fluorescence spectroscopy；Marked by the XRF of step (5) gained
Directrix curve, can draw the content of ferrum in testing sample, P elements.
Embodiment 2
1, the iron content in potassium dichromate standard solution titration measuring LiFePO4 sample:
Weigh 1.000g ± 0.005g(and be accurate to 0.0001g) lithium ion battery industry LiFePO 4 of anode material (sample 1)
In 100mL beaker, add (1+1) hydrochloric acid, after on electric furnace heated and boiled keep about 20min, close electric furnace,
Being cooled to room temperature, after filtration, constant volume is to stand-by in 100mL volumetric flask.Take solution described in 20mL, add 30mL water, 5mL(1+1) salt
Acid, is placed on electric furnace and is heated to micro-boiling, and the stannous chloride solution dripping 50g/L while hot is the most faint yellow, drips two
CuSO4-isatin indicator virescence, the TiCl of dropping 20g/L3Solution disappears to green, excess half, places solution and becomes blue
Color.Add 20mL15% sulphuric acid/phosphoric acid mixing acid, several diphenylamine sulfonic acid sodium salt indicators, titrate with potassium dichromate standard solution, molten
Liquid is become aubergine to be terminal by green transition, and consumption volume is V；Pipette Ferrous ammonium sulfate 5mL the most at twice, use and above-mentioned step
Rapid identical reagent and consumption, according to identical analytical procedure, carry out operation repetitive, consume the volume record of potassium dichromate
For V1And V2, further according to computing formula, finally give the content of ferrum element in taken LiFePO4.And parallel assay three times, make even
Average, extreme difference ＜ 3 ‰.
2, the phosphorus content during phosphorus molybdenum acid ammonium capacity method measures LiFePO4:
Weigh 1.000g ± 0.005g(and be accurate to 0.0001g) LiFePO4 (sample 1) in 100mL beaker, add (1+1) salt
Acid, after on electric furnace heated and boiled keep about 20min, close electric furnace, be cooled to room temperature, after filtration, constant volume arrives
In 100mL volumetric flask stand-by.Pipette above-mentioned solution 10mL in conical flask, be neutralized to precipitation with ammonia, then used nitric acid standard
Solution neutralization precipitation, to just disappearing, adds excess nitric acid standard solution, is slowly added to 75mL ammonium molybdate solution, and vibration 2 ~
3min, precipitation places more than 4h.Filter, wash conical flask with nitric acid standard solution and precipitate 2 ~ 3 times, then will with potassium nitrate solution
Conical flask and precipitation are all washed till neutrality.Dripping standard solution of sodium hydroxide in conical flask makes precipitation be completely dissolved, and adds 5mL
~ 10mL filters standard solution of sodium hydroxide, and record consumes sodium hydroxide volume V, adds 2 phenolphthalein indicators, use nitre after waiting
Acid standard solution residual titration becomes colorless to solution, and record volume is V1.Further according to computing formula, finally give taken LiFePO4
The content of middle P elements.And parallel assay three times, average, extreme difference ＜ 3 ‰.
Wherein, 70g/L ammonium molybdate solution is solution A (70g ammonium molybdate is dissolved in 53mL ammonia and 267mL water and making) to be delayed
Slowly pour in B solution (267mL nitric acid forms with the mixing of 400mL water), be settled to 1L.
Nitric acid concentration of standard solution is 0.1mol/L, and Concentration of Sodium Hydroxide Solution Standard is 0.1mol/L；Phthalic acid
Reagent on the basis of hydrogen potassium, phenolphthalein indicator is to weigh 1g phenolphthalein indicator to be dissolved in the dehydrated alcohol of 100mL95%.
3, preparation XRF standard sample:
Described LiFePO4 (sample 1) has passed through wet chemistry method to be tested respectively three times to average and obtains ferrum element and P elements
Content.The standard screen being used 150 mesh and 200 mesh filters out the powder sample of 150 ~ 200 mesh, the LiFePO4 that will be screened
(sample 1) is divided into six parts, is mixed into the calcium carbonate primary standard substance of different content, is configured to different iron content and different phosphate unit
The standard sample of cellulose content, wherein iron content be respectively as follows: 33.50%, 32.38%, 31.27%, 30.14%, 29.03%,
27.92%, phosphorus element content is respectively as follows: 18.85%, 18.22%, 17.59%, 16.96%, 16.34%, 15.71%.Add the most respectively
Enter quantifying glucose and make binding agent, stand-by after mixing.
4, powder pressing method compacting XRF standard sample or measuring samples:
By the LiFePO4 standard sample of six prepared gradients, in the mould such as aluminum ring being placed in diameter 30mm, uniformly pave
After pressure compaction a little, then fill full whole mould with boric acid, tablet machine apply after the pressure of 20 tons suppresses 5 seconds, pressure
Make the standard sample of lamellar.
5, the preparation of XRF standard curve:
Ferrum element and the fluorescence intensity of P elements in the standard sample being respectively compressed into tablet form with x-ray fluorescence spectrometry, and
And using the fluorescence intensity of element that measures as vertical coordinate, with the content of the ferrum element measured and P elements for horizontal seat
Mark, draws XRF standard curve.
6, arbitrary batch LiFePO4 sample ferrum element and the detection of phosphorus element content:
Choose arbitrary batch lithium ion battery anode material lithium iron phosphate sample (sample 2), the mould such as aluminum ring being placed in diameter 30mm
In tool, pressure compaction a little after uniformly paving, then fill full whole mould with boric acid, tablet machine applies the pressure of 20 tons
After suppressing 5 seconds, it is compressed into tablet form, uses x-ray fluorescence spectrometry wherein ferrum element and the fluorescence intensity of P elements, pass through
XRF standard curve draws the content of ferrum element and P elements.
Embodiment 3-5
Choose and appoint a batch of lithium ion battery anode material lithium iron phosphate sample as sample 3-5, be respectively placed in diameter 30mm
The mould such as aluminum ring in, pressure compaction a little after uniformly paving, then fill full whole mould with boric acid, tablet machine apply
After the pressure of 20 tons is suppressed 5 seconds, it is compressed into tablet form, uses X-ray fluorescence spectroscopy to record ferrum element and phosphorus unit in testing sample
The fluorescence intensity of element, and use embodiment 2 draw XRF standard curve and measure ferrum element and the content of P elements.
5 independent sample preparations and test are carried out respectively for embodiment 3, embodiment 4, embodiment 5, and 5 times are surveyed
Amount result is added up, according to the precision of relative standard deviation (RSD) the assessment present invention.The results are shown in Table 1.
Table 1 Precision Experiment (n=5) (unit: %)
As can be seen from Table 1, by the RSD(relative standard deviation of the ferrum element measured by the inventive method and P elements) it is less than
3.5%, show that method has good precision, it is good that element records result repeatability.
Above content is only to present configuration example and explanation, affiliated those skilled in the art couple
Described specific embodiment makes various amendment or supplements or use similar mode to substitute, without departing from invention
Structure or surmount scope defined in the claims, all should belong to protection scope of the present invention.
Claims (6)
1. one kind is used for measuring the fluorescence analysis method of ferrophosphorus constituent content in LiFePO4, it is characterised in that: include following step
Rapid:
(1) take same batch LiFePO4 sample, and be bisected into three parts；
(2) use first part of LiFePO4 sample of HCl treatment, after filtering unreacted carbon, form testing sample solution；With weight
It is titrated by Neutral potassium chromate standard solution, records the content of ferrum element in testing sample solution；
(3) use second part of LiFePO4 sample of HCl treatment, after filtering unreacted carbon, form testing sample solution；Use phosphorus
Ammonium molybdate volumetric method records the content of P elements in testing sample solution；
(4) the 3rd part of LiFePO4 sample is divided at least six parts, is separately added into the calcium carbonate primary standard substance of different content, joins
Make the standard sample that content is different；Use powder pressing method to be compressed into tablet form respectively by each standard sample again, then pass through X
Ray fluorescence spectrometry records ferrum, the fluorescence intensity of P elements in each lamellar standard sample；
(5) by strong by the fluorescence of ferrum in the LiFePO4 sample measured by X-ray fluorescence spectroscopy, P elements in step (4)
Degree, is associated with by ferrum, the content of P elements in the LiFePO4 sample measured by step (2), (3), is formed with fluorescence
Intensity is vertical coordinate, with ferrum, the content XRF standard curve as abscissa of P elements；
(6) use the powder pressing method identical with step (4) to be compressed into tablet form by LiFePO4 sample to be measured, obtain to be measured
Sample, records the fluorescence intensity of each element in testing sample by X-ray fluorescence spectroscopy；Marked by the XRF of step (5) gained
Directrix curve, can draw the content of ferrum in testing sample, P elements.
2. according to the fluorescence analysis method required at power described in 1, it is characterised in that: in described step (2), by first part of iron phosphate
Lithium sample adds in hydrochloric acid solution, and heated and boiled also keeps 18-25min, is then cooled to room temperature, and filters out unreacted
Carbon, the solution stannous chloride solution reduction ferric iron therein after filtration, it is subsequently adding indicator, forms solution to be measured.
3. according to the fluorescence analysis method required at power described in 2, it is characterised in that: described aqueous hydrochloric acid solution refers to that mass concentration is
The concentrated hydrochloric acid of 36% and one-level water are that 1:1 carries out mixing according to mass ratio；
Described stannous chloride solution refers to be dissolved in hydrochloric acid stannum dichloride, then to be diluted with water to concentration be 50g/L；
Described indicator is CuSO4-isatin indicator, diphenylamine sulfonic acid sodium salt indicator；Add CuSO4-isatin indicator is by yellowish
Color solution becomes green, then drips TiCl3After solution disappears to green, excess half, after placement, solution becomes blue；Add
After sulphuric acid/phosphoric acid mixing acid and diphenylamine sulfonic acid sodium salt indicator, form solution to be measured.
4. according to the fluorescence analysis method required at power described in 3, it is characterised in that: described CuSO4-isatin indicator refers to isatin
Being dissolved in aqueous sulfuric acid, then constant volume is in copper-bath；
Described TiCl3Solution refers to the titanous chloride. hydrochloric acid solution that concentration is 20g/L；
Described sulphuric acid/phosphoric acid mixing acid is the concentrated sulphuric acid of employing 95 ~ 98wt% and the phosphoric acid of 85wt% is that 1:1 mixes according to volume ratio
Close, be diluted to 1L with one-level water the most again and be made into 15wt %；
Described diphenylamine sulfonic acid sodium salt indicator refers to the diphenylamine sulfonic acid sodium water solution that concentration is 0.05g/ L.
5. according to the fluorescence analysis method required at power described in 1, it is characterised in that: described step (2) uses potassium dichromate standard
Solution titrates, and is reaction end when solution is transformed into aubergine by blueness.
6. according to the fluorescence analysis method required at power described in 1, it is characterised in that: in described step (3), filter unreacted carbon
After solution ammonia be neutralized to hydroxide precipitation and occurred, then with in nitric acid standard solution and hydroxide precipitation, and make
It just disappears；Being subsequently adding excess nitric acid standard solution, be slowly added to ammonium molybdate solution, vibrate 2 ~ 3min postprecipitation, and puts
Put more than 4h, obtain the content of wherein P elements.
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