CN100575934C - The quantitative analysis method of crystalline phase cobalt/cobalt oxide content in a kind of lithium and cobalt oxides - Google Patents
The quantitative analysis method of crystalline phase cobalt/cobalt oxide content in a kind of lithium and cobalt oxides Download PDFInfo
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- CN100575934C CN100575934C CN200510069061A CN200510069061A CN100575934C CN 100575934 C CN100575934 C CN 100575934C CN 200510069061 A CN200510069061 A CN 200510069061A CN 200510069061 A CN200510069061 A CN 200510069061A CN 100575934 C CN100575934 C CN 100575934C
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Abstract
A kind of quantitative analysis method as crystalline phase cobalt/cobalt oxide content in the lithium and cobalt oxides of anode material for lithium-ion batteries comprises coefficient of determination K value, calculates the quality percentage composition W of crystalline phase cobalt/cobalt oxide in the lithium and cobalt oxides that contains the crystalline phase cobalt/cobalt oxide that is mixed with internal standard compound matter
(cobalt/cobalt oxide)And according to above-mentioned K value and W
(cobalt/cobalt oxide)Value is calculated three steps of content of crystalline phase cobalt/cobalt oxide in the lithium and cobalt oxides.Adopt method of the present invention can accurately judge the crystal phase structure of cobalt/cobalt oxide, and can go out the content of crystalline phase cobalt/cobalt oxide in the lithium and cobalt oxides with higher accuracy quantitative measurement.
Description
Technical field
The invention relates to a kind of lithium and cobalt oxides (LiCoO
2) in the analytical approach of crystalline phase cobalt/cobalt oxide, more specifically say so about a kind of quantitative analysis method as crystalline phase cobalt/cobalt oxide content in the lithium and cobalt oxides of anode material for lithium-ion batteries.
Background technology
Lithium and cobalt oxides has two-dimensional layered structure, suitable lithium ion take off embedding, and because its preparation technology is easy, stable performance, specific storage height, good cycle, a large amount of at present as commercial anode material for lithium-ion batteries.
The synthetic method of lithium and cobalt oxides has a variety of, and modal in the production is high temperature solid phase synthesis: with Li
2O
3(or Li
2CO
3) and CoCO
3(or Co
3O
4) be raw material, press Li: Co=1: the preparation of 1 mol ratio, under 700-900 ℃, carry out pre-service, it is broken to carry out gas then, and calcination forms in 700-900 ℃ of following air atmosphere again.In concrete production practices, because the batch process amount is big, the process control accidentalia is many, presses Li: Co=1: when 1 mol ratio is prepared primary raw materials, if do not regulate and control, be difficult to guarantee not residual crystalline phase cobalt/cobalt oxide (Co in the end product in pre-treatment step
3O
4, Co
2O
3And/or CoO).And these crystalline phase cobalt/cobalt oxides can not provide lithium ion to take off embedding, poor electric conductivity, and its existence will seriously reduce the electrochemical activity of lithium and cobalt oxides, greatly influence specific storage, cycle performance and the serviceable life of lithium ion battery.Therefore when producing lithium and cobalt oxides in batches, controlling and eliminate crystalline phase cobalt/cobalt oxide residual in the lithium and cobalt oxides effectively is one of key of this technology.
In addition, along with the poorness day by day of cobalt resource, reclaim the cobalt, the regeneration LiCoO that scrap in the anode material for lithium-ion batteries
2Active material concerning lithium ion battery manufacturing enterprise, has suitable economic return potentiality.Owing to cause the lithium ion battery failure reasons varied, such as battery overcharge inefficacy, internal short-circuit of battery inefficacy, battery explosion etc., they all can produce the crystalline phase cobalt/cobalt oxide in positive electrode.Regenerate again has the lithium and cobalt oxides of electrochemical activity, not only needs to know whether to have the crystalline phase cobalt/cobalt oxide, more needs accurately to analyze the content of crystalline phase cobalt/cobalt oxide.
In the prior art, crystalline phase cobalt/cobalt oxide content mainly is by utilizing in plasma (ICP) emission spectrometer, the atomic absorption spectrophotometer (AAS) instrument and equipment test materials such as (AAS) total lithium, cobalt content to calculate indirectly in the lithium and cobalt oxides material, is a kind of qualitative judgement method.For example, measure LiCoO with ICP
2During crystalline phase cobalt/cobalt oxide content, can only at first determine the content of elemental lithium in the lithium and cobalt oxides, cobalt element, calculate the mol ratio lithium of lithium cobalt element then: cobalt is 1: M, qualitatively judge again at last, when M=1, judge LiCoO
2Sample is pure product; When M＞1, judge LiCoO
2Containing cobalt/cobalt oxide impurity in the sample, is Co but can not judge this crystalline phase cobalt/cobalt oxide
3O
4, Co
2O
3And/or CoO.And in fact, because it is armorphous (because armorphous compound does not have the fixedly crystal phase structure of poor electric conductivity, the normal electrode reaction that participates in battery, help the electron transport of battery, do not need control and eliminate) or the existence of other lithium-containing compounds, cobalt compound, with crystalline phase cobalt/cobalt oxide content qualitative judgement result that above-mentioned analytical approach drew often with the lithium and cobalt oxides material in the real content of crystalline phase cobalt/cobalt oxide deviate from mutually.
Summary of the invention
The objective of the invention is to can not determine that in order to solve measuring technologies such as ICP of the prior art, AAS the crystal phase structure of cobalt/cobalt oxide in the lithium and cobalt oxides material reaches the shortcoming to the inferred results poor accuracy of crystalline phase cobalt/cobalt oxide content, a kind of quantitative analysis method that can determine the cobalt/cobalt oxide crystal phase structure and measure crystalline phase cobalt/cobalt oxide content in the lithium and cobalt oxides with higher accuracy is provided.
The quantitative analysis method of crystalline phase cobalt/cobalt oxide content may further comprise the steps in the anode active material of lithium ion battery lithium and cobalt oxides provided by the invention:
(1) measures M with the XRD diffractometer
(standard substance): M
(interior mark)Be n: the diffraction spectrogram of 1 the potpourri that contains standard substance and internal standard compound matter, and calculate the intensity I of a diffraction peak of standard substance
(standard substance)Intensity I with a diffraction peak of internal standard compound matter
(interior mark), (1) design factor K value by formula,
K=I
(standard substance)M
(interior mark)/ I
(interior mark)M
(standard substance)=I
(standard substance)/ nI
(interior mark)(1),
Wherein, M
(standard substance)And M
(interior mark)Be respectively the quality percentage composition of standard substance and the quality percentage composition of internal standard compound matter, n is 1-10, and standard substance is crystalline phase Co
3O
4, Co
2O
3Or CoO, internal standard compound matter does not produce the pure crystalline phase material of interference to standard substance to the small part diffraction peak for its diffraction peak;
(2) use method identical and identical measuring condition to measure M with above-mentioned steps (1)
o (lithium cobalt oxidation Thing): M
o (interior mark)Be n
o: the diffraction spectrogram of 1 the lithium and cobalt oxides that contains the crystalline phase cobalt/cobalt oxide and the potpourri of internal standard compound matter, and calculate and above-mentioned steps (1) in the intensity I of diffraction peak of crystalline phase cobalt/cobalt oxide of standard substance diffraction peak same position
o (cobalt/cobalt oxide)With with above-mentioned steps (1) in the intensity I of diffraction peak of internal standard compound matter of internal standard compound matter diffraction peak same position
o (interior mark), by formula (2) calculate W
(cobalt/cobalt oxide):
W
(cobalt/cobalt oxide)=I
o (cobalt/cobalt oxide)W
(interior mark)/ I
o (interior mark)K (2),
Wherein, M
o (lithium and cobalt oxides)And M
o (interior mark)Be respectively the quality percentage composition of the lithium and cobalt oxides that contains the crystalline phase cobalt/cobalt oxide and the quality percentage composition of internal standard compound matter, n
oBe 1-10, W
(interior mark)Be the quality percentage composition of internal standard compound matter in the potpourri of the lithium and cobalt oxides that contains the crystalline phase cobalt/cobalt oxide and internal standard compound matter, W
(cobalt/cobalt oxide)Quality percentage composition for crystalline phase cobalt/cobalt oxide in the potpourri of the lithium and cobalt oxides that contains the crystalline phase cobalt/cobalt oxide and internal standard compound matter;
(3) calculate M by following formula (3)
(cobalt/cobalt oxide):
M
(cobalt/cobalt oxide)=W
(cobalt/cobalt oxide)/ (1-W
(interior mark)) (3),
Wherein, M
(cobalt/cobalt oxide)Represent the quality percentage composition of crystalline phase cobalt/cobalt oxide in the lithium and cobalt oxides that contains the crystalline phase cobalt/cobalt oxide.
Adopt method of the present invention can accurately judge the structure of crystalline phase cobalt/cobalt oxide, and can go out the content of crystalline phase cobalt/cobalt oxide in the lithium and cobalt oxides with higher accuracy quantitative measurement.When the condition determination of XRD diffractometer be graphite monochromator, copper target use power be 800 watts, the sweep velocity of angular instrument be 4 degree/minute, sweep limit 2 θ=10 °-75 °, when the scanning step, the footpath was 0.020 degree/step, the crystalline phase Co of 5 weight %
3O
4Determination on content result's relative error is less than 11%, the crystalline phase Co of 10-25 weight %
3O
4Determination on content result's relative error is less than 6% (referring to embodiment 1); When the condition determination of XRD diffractometer be graphite monochromator, copper target use power be 1600 watts, the sweep velocity of angular instrument be 2 degree/minute, sweep limit 2 θ=15 °-50 °, when the scanning step, the footpath was 0.010 degree/step, be equal to or less than 5% crystalline phase Co
3O
4Determination on content result's relative error is less than 5%, the crystalline phase Co of 10-25 weight %
3O
4Determination on content result's relative error is less than 2% (referring to embodiment 2); When the condition determination of XRD diffractometer be graphite monochromator, copper target use power be 1600 watts, the sweep velocity of angular instrument be 2 degree/minute, sweep limit 2 θ=15 °-50 °, when the scanning step, the footpath was 0.010 degree/step, the crystalline phase CoO Determination on content result's of 10-40 weight % relative error is 11% (referring to embodiment 3) less than the crystalline phase CoO Determination on content result's of 4%, 5 weight % relative error.
The x-ray source that experiment showed, the XRD diffractometer uses power high more, and the integrated intensity of diffraction peak is just strong more, and the detection limit when using the inventive method to measure crystalline phase cobalt/cobalt oxide content in the lithium and cobalt oxides is just low more; Sweep velocity is slow more, scanning step footpath is more little, and the integrated intensity fluctuation of diffraction peak is little, and the reappearance of measurement result and accuracy are just high more.
The above results shows, quantitative analysis method provided by the present invention has successfully solved the shortcoming that prior art (ICP, AAS etc.) be can not determine the crystal phase structure and the crystalline phase cobalt/cobalt oxide content inferred results poor accuracy of cobalt/cobalt oxide in the lithium and cobalt oxides, and its accuracy of measurement can satisfy the production and the control needs of lithium and cobalt oxides material.
Description of drawings
Fig. 1 contains internal standard compound matter Si powder and standard substance crystalline phase Co among the embodiment 1
3O
4The XRD diffraction spectrogram of potpourri;
Fig. 2 is for containing the crystalline phase Co of different content among the embodiment 1
3O
4Lithium and cobalt oxides and the XRD diffraction spectrogram series comparison diagram of the potpourri of internal standard compound matter Si powder;
Fig. 3 contains internal standard compound matter Si powder and standard substance crystalline phase Co among the embodiment 2
3O
4The XRD diffraction spectrogram of potpourri;
Fig. 4 is for containing the crystalline phase Co of different content among the embodiment 2
3O
4Lithium and cobalt oxides and the XRD diffraction spectrogram series comparison diagram of the potpourri of internal standard compound matter Si powder;
Fig. 5 is for containing the XRD diffraction spectrogram of the potpourri of internal standard compound matter NaCl powder and standard substance crystalline phase CoO among the embodiment 3;
Fig. 6 is the lithium and cobalt oxides and the serial comparison diagram of the XRD diffraction spectrogram of the potpourri of internal standard compound matter NaCl powder of the crystalline phase CoO that contains different content among the embodiment 3;
The strongest diffraction peak of label symbol 1 expression crystalline phase Si powder internal standard compound matter among the above-mentioned figure, 2 expression crystalline phase Co
3O
4The strongest diffraction peak, the strongest diffraction peak of 3 expression crystalline phase NaCl powder internal standard compound matter, the strongest diffraction peak of 4 expression crystalline phase CoO.
Embodiment
According to method provided by the invention, described internal standard compound matter can select for use its diffraction peak at least the part diffraction peak of crystalline phase cobalt/cobalt oxide not to be produced the crystalline phase material of interference, as pure Si powder, α-SiO
2Powder, MgO, CaF
2, BaCO
3, TiO
2(rutile), KCl, NaCl, Fe
3O
4, ZnO, CaO, NaF, NiO or α-Al
2O
3Powder.
The described pure purity that is meant is not less than 99 weight %.Under the preferable case, described internal standard compound matter is selected the crystalline phase material that the strongest diffraction peak of crystalline phase cobalt/cobalt oxide is not produced interference for use.For example, when the crystalline phase cobalt/cobalt oxide of being measured be Co
3O
4The time, it is suitable that the Si powder of selecting for use purity to be not less than 99 weight % is made internal standard compound matter, should not use α-SiO
2, because α-SiO
2A diffraction peak to Co
3O
4The strongest diffraction peak produce and disturb, influence precision of test result; When the crystalline phase cobalt/cobalt oxide of being measured was CoO, selecting for use purity to be not less than 99% NaCl powder, to make internal standard compound matter be suitable, should not use α-SiO
2, because α-SiO
2A diffraction peak overlapping substantially to the strongest diffraction peak of CoO, greatly influence precision of test result.
Described standard substance is selected from crystalline phase Co
3O
4, Co
2O
3Or CoO, crystalline phase Co in needs quantitative test lithium and cobalt oxides
3O
4During content, select Co for use
3O
4Make standard substance; Need crystalline phase Co in the quantitative test lithium and cobalt oxides
2O
3During content, select Co for use
2O
3Make standard substance; When needing in the quantitative test lithium and cobalt oxides crystalline phase CoO content, select for use CoO to make standard substance.
According to method of the present invention, described crystalline phase cobalt/cobalt oxide is meant crystalline phase Co
3O
4, Co
2O
3And/or CoO, if contain wherein two or three simultaneously, when quantitative test, can adopt uses the same method measures respectively.
The ratio of the quality percentage composition of standard substance and the quality percentage composition of internal standard compound matter is n: 1, and wherein n is 1-10, preferred n is 1-4.
The ratio that contains the quality percentage composition of the quality percentage composition of lithium and cobalt oxides of crystalline phase cobalt/cobalt oxide and internal standard compound matter is n
o: 1, n wherein
oBe 1-10, preferred n
oBe 1-4; And n
oCan equate with n also can be unequal.
Described internal standard compound matter, standard substance, the lithium and cobalt oxides that contains the crystalline phase cobalt/cobalt oxide are Powdered, and their grain size should meet the scope that the XRD diffractometer requires, in general, and their mean grain size D
50=1-15 micron is preferably D
50=2-12 micron (D
50Be the size-grade distribution index, the mean grain size of expression size-grade distribution).Can adopt known method and technology, above-mentioned substance be handled so that its mean grain size reaches requirement as grind, gas is broken etc.Mean grain size can select for use various laser particle size distribution instrument of the prior art to measure.
Among the present invention, the potpourri that will contain the potpourri of internal standard compound matter and standard substance, the lithium and cobalt oxides that contains the crystalline phase cobalt/cobalt oxide and internal standard compound matter is made test piece and is carried out the XRD diffraction and measure, the making of test piece can be adopted various method for makings in the prior art, the present invention preferably adopts pressed disc method, being about to standard model framework (as aluminium quality sample framework) lies against on the glass planar, test surfaces is downward, in the groove of sample framework, fill up testing sample and compacting, remove unnecessary material, remove the sample framework, obtain being parallel to the test surfaces on sample framework surface.
The method according to this invention, all preparation test pieces on the standard model framework, its test surfaces should not have preferred orientation, can realize by following method of the prior art: position phase rubbing method, the fill method that improves sample, the method that adds thinning agent in sample or employing rotation backswing sample bench.Preferably adopt the method that in sample, adds thinning agent to eliminate preferred orientation in embodiments of the present invention
According to method of the present invention, the intensity of the diffraction peak of internal standard compound matter, standard substance, crystalline phase cobalt/cobalt oxide can and well known to a person skilled in the art calculated in various ways with XRD diffractometer in the prior art, calculate as height intensity, areal intensity or integrated intensity with diffraction peak, the preferred integrated intensity that uses in the specific embodiment of the invention, promptly that calculate, that represent with tale, the deduction back of the body end by computer control and carry out x-ray source K α 1 and K α 2 line separating treatment after the integrated intensity of the diffracted ray that causes of deduction K α 2 lines.The alternate figures solution (R method) that described K α 1 and K α 2 line separating treatment can adopt Rachinger to propose, the Fourier converter technique that also can adopt Gangulee to propose is handled; The present invention adopts the R method to handle, and is to utilize JADE (5.0) diffraction data process software to calculate and deduct processing in the specific embodiment.
Diffraction peak described in the present invention can be the strongest diffraction peak, it also can be the diffraction peak of other intensity orders, but necessary the assurance: in same test and data handling procedure, the diffraction peak of the middle internal standard compound matter of the diffraction peak of internal standard compound matter and step (1) is that the diffraction peak of same position, the diffraction peak of the middle crystalline phase cobalt/cobalt oxide of step (2) and the diffraction peak of the middle standard substance of step (1) are the diffraction peak of same position in the inventive method step (2); But under same condition determination, the intensity of diffraction peak is low more, and the detection limit of measurement result and sensitivity are also low more, so the preferred integrated intensity that adopts the diffraction peak of integrated intensity maximum comes the content of design factor K and crystalline phase cobalt/cobalt oxide in the embodiment of the invention.
Described X diffractometer can be the X-ray diffractometer that comprehensive stability is better than any model of 1%.The comprehensive stability of described x-ray powder diffraction instrument be better than 1% be meant the proper testing condition (source current fluctuation less than 10%, mains fluctuations less than 10%, environment temperature (room temperature) do not have acute variation and fixing apparatus measures parameter) under, the strongest diffraction peak of replication single crystalline Si powder standard model, its standard deviation of the integrated intensity of strong diffraction peak less than 1%.
According to method provided by the invention, the condition determination of described XRD diffractometer comprises: monochromaticity x-ray source copper target (also available iron target, cobalt target, tungsten target, molybdenum target or manganese target, it uses power to decide according to the design power of different targets), the power that uses of copper target is 400-3000 watt, is preferably 800-3000 watt; The sweep velocity of angular instrument be the 0.01-8.00 degree/minute, preferred 1.00-4.00 degree/minute, sweep limit 2 θ=5 °-160 °, preferred 10 °-80 °, scanning step footpath 0.010-0.040 degree/step, preferably 0.010-0.020 degree/step.
According to method provided by the invention, the X-ray source of XRD diffractometer can be selected copper target, iron target, cobalt target, tungsten target, molybdenum target or manganese target etc. for use, different targets will cause 2 θ angles of diffraction peak that corresponding the change taken place, the K value is also ensued variation, but for same lithium and cobalt oxides sample, different targets is to not influence of crystalline phase cobalt/cobalt oxide Determination on content result.
According to method provided by the invention, the mode that can use graphite monochromator or add filter disc in light path makes the X ray monochromatization, to obtain the high x-ray source of monochromaticity.Owing in light path, add the greatly diffracted intensity of lowering apparatus of filter disc, so the present invention uses preferably graphite monochromator to make the X ray monochromatization.
As long as guarantee that the X source of sufficient intensity is arranged, good instrument comprehensive stability (being better than 1%), high instrumental resolution be (in high angle of diffraction, promptly concerning the copper target, 2 θ are in 50 ° of-80 ° of scopes, can obtain and differentiate two K α 1 and K α 2 lines clearly), those skilled in the art also can select other measuring conditions.
According to method provided by the invention, increase the intensity of x-ray source, promptly improve the use power of X-ray pipe, will improve the detection limit and the sensitivity of instrument greatly; Reduce sweep velocity, reduce scanning step footpath, will help improving the stable and repeated of test result, referring to the embodiment of the invention 2.
According to method provided by the invention, (n is 1-10, n in certain test specification
oBe 1-10), the wavelength X of the X-ray source that the K value only adopts with the XRD diffractometer and 2 θ angles of diffraction peak are relevant, and with n and/or n
oValue is irrelevant, therefore changes n and/or n in above-mentioned scope
oValue is to the not influence of measurement result accuracy.
The method according to this invention, the computing method of relative error are method commonly known in the art, and promptly computing formula is: (actual value-measured value)/actual value.
Method provided by the invention can be used for measuring crystalline phase cobalt/cobalt oxide content in the lithium and cobalt oxides of prepared in various methods.
In addition, can also adopt method provided by the invention to monitor in the technological process content of crystalline phase cobalt/cobalt oxide in the lithium and cobalt oxides, thereby provide foundation for subsequent technique.When for example firing (or regeneration) lithium and cobalt oxides at high temperature solid phase synthesis, can the phase one (pretreatment stage) promptly adjust size-grade distribution, exterior appearance, when evenly mixing, utilize the XRD diffractometer accurately to measure the content of crystalline phase cobalt/cobalt oxide residual in the lithium and cobalt oxides, with accurate adjustment Li source (Li
2O
3Or Li
2CO
3) inventory, thereby guarantee neither to contain the crystalline phase cobalt/cobalt oxide in the lithium and cobalt oxides through after subordinate phase the firing of (finished product stage), do not make Li simultaneously again
2O
3(or Li
2CO
3) excessive too many, reach the purpose that improves the lithium and cobalt oxides quality, but also help reducing the washing process process of back, save production cost greatly.
Equally, the content of the crystalline phase cobalt/cobalt oxide of scrapping in the anode material for lithium-ion batteries can be accurately measured in the quantitative analysis method of the application of the invention, and handling for the subsequent regeneration of lithium ion battery provides foundation.
The following examples will the invention will be further described.
Used XRD diffractometer: the D/MAX2200PC type XRD diffractometer that Japanese company of science produces;
The condition determination of XRD diffractometer comprises: the wavelength X of x-ray source=1.54056 dusts (Cu/K α 1), the use power of copper target are 40 kilovolts, 20 milliamperes (promptly 800 watts); Graphite monochromator; The sweep velocity of angular instrument be 4 degree/minute, sweep limit 2 θ=10 °-75 °, in the 0.020 degree/step of scanning step footpath, scan mode is θ/2 θ linked scans; Light path slit system parameter is provided with: divergent slit is that 1 °, anti-scatter slit are that 10 millimeters, variable gap are that to adjust, receive slit automatically be 0.3 millimeter to instrument;
The instrument data process software is: MDI-JADE (5.0);
Internal standard compound matter: purity is the Si powder of 99 weight %, and U.S. Sigma-aldrich company produces;
Standard substance: purity is the Co of 99 weight %
3O
4Crystal powder;
Lithium and cobalt oxides: do not contain crystalline phase Si and/or Co
3O
4LiCoO
2Powder;
n＝2、n
o＝2；
Determination step:
(1) measures M with the XRD diffractometer
(standard substance): M
(interior mark)Be the Co that contains of 2: 1 (being n=2)
3O
4The XRD diffraction spectrogram of the potpourri of standard substance and Si powder internal standard compound matter, design factor K value;
Concrete operations are as follows:
A) with 3.500 gram Si powder internal standard compound matter and 2.0000 Co that restrain
3O
4Standard substance grinds with agate mortar respectively, and the mean grain size that records the two with laser particle size distribution instrument is respectively D
50=10.980 microns and D
50=4.089 microns;
B) accurately take by weighing 0.5000 above-mentioned Si powder internal standard compound matter of gram and the above-mentioned Co of 1.0000 grams
3O
4Standard substance grinds in agate mortar, makes uniform mix, and the mean grain size that records potpourri with laser particle size distribution instrument is D
50=5.207 microns;
C) standard aluminum quality sample framework is lain against on the glass planar, test surfaces is downward, fills up above-mentioned M in the groove (20 millimeters * 18 millimeters * 2 millimeters) of sample framework
(standard substance): M
(interior mark)Be 2: 1 the Co that contains
3O
4The potpourri of standard substance and Si powder internal standard compound matter, and compacting, remove unnecessary material, remove aluminium quality sample framework, obtain having the test piece of the test surfaces that is parallel to sample framework surface;
D) measure the above-mentioned Co that contains with the XRD diffractometer
3O
4The XRD diffraction spectrogram of the test piece of the potpourri of standard substance and Si powder internal standard compound matter, and with MDI-JADE (5.0) data processing software, after separating and deduct diffracted ray that K α 2 lines cause, deduct treatment steps such as carrying on the back the end through level and smooth, K α 1 and K α 2 lines, accurately measure the integrated intensity I of the strongest diffraction peak 1 of Si powder internal standard compound matter
(interior mark), Co
3O
4The integrated intensity I of the strongest diffraction peak 2 of standard substance
(standard substance), gained XRD diffraction spectrogram as shown in Figure 1, wherein
I
(interior mark)=6388 (Counts); I
(standard substance)=6809 (Counts)
E) with n=2, I
(interior mark)=6388 (Counts), I
(standard substance)=6809 (Counts) substitution formula (1)
K=I
(standard substance)M
(interior mark)/ I
(interior mark)M
(standard substance)=I
(standard substance)/ nI
(interior mark)(1) calculates COEFFICIENT K=0.5330;
(2) use method identical and identical measuring condition to measure M with above-mentioned steps (1)
o (lithium cobalt oxidation Thing): M
o (interior mark)Be 2: 1 (be n
o=2) contain crystalline phase Co
3O
4Lithium and cobalt oxides and the diffraction spectrogram of the potpourri of Si powder internal standard compound matter, calculate crystalline phase Co
3O
4The quality percentage composition
:
Concrete operations are as follows:
A) take by weighing 6.0000 gram LiCoO
2Powder grinds in agate mortar, and getting mean grain size is D
50=5.429 microns pressed powder;
B) five parts of weight are mean grain size D described in 0.5000 above-mentioned steps (1) that restrains
50=10.980 microns the Si powder internal standard compound matter and the above-mentioned LiCoO of the described quality of table 1
2Mean grain size D described in powder and the step (1)
50=4.089 microns Co
3O
4Standard substance grinds in agate mortar evenly, makes the crystalline phase Co that contains known content
3O
4Lithium and cobalt oxides and the potpourri of Si powder internal standard compound matter;
Table 1 contains crystalline phase Co
3O
4Lithium and cobalt oxides and the composition of the potpourri of Si powder internal standard compound matter
C) standard aluminum quality sample framework is lain against on the glass planar, test surfaces is downward, fills up each M in the above-mentioned table 1 in the groove (20 millimeters * 18 millimeters * 2 millimeters) of sample framework
o (lithium and cobalt oxides): M
o (in Mark)Be 2: 1 contain crystalline phase Co
3O
4Lithium and cobalt oxides and the potpourri of Si powder internal standard compound matter, and compacting, remove unnecessary material, remove aluminium quality sample framework, obtain having the test piece of the test surfaces that is parallel to sample framework surface;
D) contain crystalline phase Co with above-mentioned each of XRD diffractometer sequentially determining
3O
4Lithium and cobalt oxides and the XRD diffraction spectrogram of the test piece of the potpourri of Si powder internal standard compound matter, and with MDI-JADE (5.0) data processing software, after separating and deduct diffracted ray that K α 2 lines cause, deduct treatment steps such as carrying on the back the end through level and smooth, K α 1 and K α 2 lines, obtain containing crystalline phase Co
3O
4Lithium and cobalt oxides and the sample 1 of the potpourri of Si powder internal standard compound matter
#-5
#The XRD diffraction spectrogram, as shown in Figure 2, wherein contain crystalline phase Co
3O
4Lithium and cobalt oxides and the potpourri of Si powder internal standard compound matter in crystalline phase Co
3O
4The integrated intensity of the strongest diffraction peak 2
Integrated intensity I with the strongest diffraction peak 1 of Si powder internal standard compound matter
o (Si)As shown in table 2 respectively;
E) will contain crystalline phase Co
3O
4Lithium and cobalt oxides and the potpourri of Si powder internal standard compound matter in the quality percentage composition W of Si powder internal standard compound matter
(Si)Shown in=0.5000/ (1.0000+0.5000)=33.33%, the table 2
And I
o (Si)Numerical value substitution formula (2)
Calculate and contain crystalline phase Co
3O
4Lithium and cobalt oxides and the potpourri of Si powder internal standard compound matter in crystalline phase Co
3O
4The quality percentage composition
Result of calculation is shown in the table 2;
(3) with gained in the step (2)
With W
(Si)The following formula of substitution (3) calculates and contains crystalline phase Co
3O
4Lithium and cobalt oxides series in crystalline phase Co
3O
4The quality percentage composition
Result of calculation is as shown in table 2, wherein
For containing crystalline phase Co
3O
4Lithium and cobalt oxides in crystalline phase Co
3O
4The quality percentage composition.
Table 2 contains crystalline phase Co
3O
4Lithium and cobalt oxides and the potpourri series of Si powder internal standard compound matter in crystalline phase Co
3O
4Determination on content result
Annotate: 1.
For containing Co
3O
4Lithium and cobalt oxides in Co
3O
4Actual content
Repeat the step measurements Co of the foregoing description 1
3O
4Content is respectively 1%, 2%, 5%, 10%, 20%, 25% LiCoO
2Crystalline phase Co in the powder
3O
4Content, different is: the use power of XRD diffractometer is 1600 watts, the sweep velocity of angular instrument be 2 degree/minute, sweep limit 2 θ=15 °-50 °, 0.010 degree/step of scanning step footpath; Si powder internal standard compound matter and Co in the step (1)
3O
4The mean grain size D of the potpourri of standard substance
50=7.357 microns; The XRD diffraction spectrogram that records as shown in Figure 3, the integrated intensity I of the strongest diffraction peak 1 of internal standard compound matter Si powder wherein
(interior mark)=20906 (Counts), Co
3O
4The integrated intensity I of the strongest diffraction peak 2 of standard substance
(standard substance)=27268 (Counts); COEFFICIENT K=0.6522; Step contains crystalline phase Co in (2)
3O
4The lithium and cobalt oxides and the composition of the potpourri of Si powder internal standard compound matter as shown in table 3, its XRD diffraction spectrogram wherein contains crystalline phase Co as shown in Figure 4
3O
4Lithium and cobalt oxides and the potpourri of Si powder internal standard compound matter in crystalline phase Co
3O
4The integrated intensity of the strongest diffraction peak 2
The integrated intensity I of the strongest diffraction peak 1 of Si powder internal standard compound matter
o (Si), contain crystalline phase Co
3O
4Lithium and cobalt oxides and the potpourri of Si powder internal standard compound matter in crystalline phase Co
3O
4The quality percentage composition
And contain crystalline phase Co
3O
4Lithium and cobalt oxides in crystalline phase Co
3O
4The quality percentage composition
Result of calculation such as table 4.
Table 3 contains crystalline phase Co
3O
4Lithium and cobalt oxides and the composition of the potpourri of Si powder internal standard compound matter
Table 4 contains crystalline phase Co
3O
4Lithium and cobalt oxides and the potpourri series of Si powder internal standard compound matter in crystalline phase Co
3O
4Determination on content result
Annotate: 1.
For containing Co
3O
4Lithium and cobalt oxides in Co
3O
4Real content
The test result of embodiment 1,2 shows: improve target power, reduce sweep velocity, reduce scanning step footpath, will increase substantially the sensitivity and the repeatability of test result.
The step measurements crystalline phase CoO content that repeats the foregoing description 1 is the content of crystalline phase CoO in 5%, 10%, 20%, 30% and 40% the lithium and cobalt oxides, and different is:
The condition determination of XRD diffractometer: with embodiment 2;
Internal standard compound matter: mean grain size D
50=9.440 microns, purity are the crystal NaCl powder of 99 weight %;
Standard substance: mean grain size is that D50=3.462 micron, purity are the crystal CoO powder of 99 weight %;
n＝1，n
o＝1；
The mean grain size D of the potpourri of NaCl powder internal standard compound matter and CoO standard substance
50=2.430 microns;
Lithium and cobalt oxides: the LiCoO that does not contain NaCl and/or CoO crystalline phase
2Powder;
In the step (1) gained XRD diffraction spectrogram as shown in Figure 5, the integrated intensity I of the strongest diffraction peak 3 of internal standard compound matter NaCl powder wherein
(interior mark)=49143 (Counts), the integrated intensity I of the strongest diffraction peak 4 of CoO standard substance
(standard substance)=25814 (Counts); COEFFICIENT K=0.5253; The composition of potpourri that contains the lithium and cobalt oxides of crystalline phase CoO and NaCl powder internal standard compound matter in the step (2) is as shown in table 5, its XRD diffraction spectrogram as shown in Figure 5, contain the lithium and cobalt oxides of crystalline phase CoO and NaCl powder internal standard compound matter potpourri the XRD diffraction spectrogram as shown in Figure 6, the integrated intensity I of the strongest diffraction peak 4 of crystalline phase CoO wherein
o (CoO), the strongest diffraction peak 3 of NaCl powder internal standard compound matter integrated intensity I
o (NaCl), contain the quality percentage composition W of crystalline phase CoO in the potpourri of the lithium and cobalt oxides of crystalline phase CoO and NaCl powder internal standard compound matter
(CoO)And contain the quality percentage composition M of crystalline phase CoO in the lithium and cobalt oxides of crystalline phase CoO
(CoO)Result of calculation such as table 6.
Table 5 contains the composition of the potpourri of the lithium and cobalt oxides of crystalline phase CoO and NaCl powder internal standard compound matter
Table 6 contains crystalline phase CoO Determination on content result in the potpourri series of the lithium and cobalt oxides of crystalline phase CoO and NaCl powder internal standard compound matter
Annotate: 1.M
1 (CoO)Real content for CoO in the lithium and cobalt oxides that contains CoO
2. relative error=(M
(CoO)-M
1 (CoO))/M
1 (CoO)
Claims (10)
1. the quantitative analysis method of crystalline phase cobalt/cobalt oxide content in the lithium and cobalt oxides is characterized in that this method comprises:
(1) measures M with the XRD diffractometer
(standard substance): M
(interior mark)Be n: the diffraction spectrogram of 1 the potpourri that contains standard substance and internal standard compound matter, and calculate the intensity I of a diffraction peak of standard substance
(standard substance)Intensity I with a diffraction peak of internal standard compound matter
(interior mark), (1) design factor K value by formula,
K=I
(standard substance)M
(interior mark)/ I
(interior mark)M
(standard substance)=I
(standard substance)/ nI
(interior mark)(1), wherein, M
(standard substance)And M
(interior mark)Be respectively the quality percentage composition of standard substance and the quality percentage composition of internal standard compound matter, n is 1-10, and standard substance is crystalline phase Co
3O
4, Co
2O
3Or CoO, internal standard compound matter does not produce the pure crystalline phase material of interference to standard substance to the small part diffraction peak for its diffraction peak;
(2) use method identical and identical measuring condition to measure M with above-mentioned steps (1)
o (lithium cobalt oxidation Thing): M
o (interior mark)Be n
o: the diffraction spectrogram of 1 the lithium and cobalt oxides that contains the crystalline phase cobalt/cobalt oxide and the potpourri of internal standard compound matter, and calculate and above-mentioned steps (1) in the intensity I of diffraction peak of crystalline phase cobalt/cobalt oxide of standard substance diffraction peak same position
o (cobalt/cobalt oxide)With with above-mentioned steps (1) in the intensity I of diffraction peak of internal standard compound matter of internal standard compound matter diffraction peak same position
o (interior mark), by formula (2) calculate W
(cobalt/cobalt oxide):
W
(cobalt/cobalt oxide)=I
o (cobalt/cobalt oxide)W
(interior mark)/ I
o (interior mark)K (2),
Wherein, M
o (lithium and cobalt oxides)And M
o (interior mark)Be respectively the quality percentage composition of the lithium and cobalt oxides that contains the crystalline phase cobalt/cobalt oxide and the quality percentage composition of internal standard compound matter, n
oBe 1-10, W
(interior mark)Be the quality percentage composition of internal standard compound matter in the potpourri of the lithium and cobalt oxides that contains the crystalline phase cobalt/cobalt oxide and internal standard compound matter, W
(cobalt/cobalt oxide)Quality percentage composition for crystalline phase cobalt/cobalt oxide in the potpourri of the lithium and cobalt oxides that contains the crystalline phase cobalt/cobalt oxide and internal standard compound matter;
(3) calculate M by following formula (3)
(cobalt/cobalt oxide):
M
(cobalt/cobalt oxide)=W
(cobalt/cobalt oxide)/ (1-W
(interior mark)) (3),
Wherein, M
(cobalt/cobalt oxide)Represent the quality percentage composition of crystalline phase cobalt/cobalt oxide in the lithium and cobalt oxides that contains the crystalline phase cobalt/cobalt oxide.
2. analytical approach according to claim 1, wherein, n is 1-4.
3. analytical approach according to claim 1, wherein, n
oBe 1-4.
4. analytical approach according to claim 1, wherein, described internal standard compound matter is crystalline phase Si powder, α-SiO
2Powder, MgO, CaF
2, BaCO
3, TiO
2, KCl, NaCl, Fe
3O
4, ZnO, CaO, NaF, NiO or α-Al
2O
3Powder.
5. analytical approach according to claim 1, wherein, when the crystalline phase cobalt/cobalt oxide is Co
3O
4The time, internal standard compound matter is the crystalline phase Si powder that purity is not less than 99 weight %; When the crystalline phase cobalt/cobalt oxide was CoO, internal standard compound matter was the crystalline phase NaCl powder that purity is not less than 99 weight %.
6. analytical approach according to claim 1, wherein, the target of described XRD diffractometer is copper target, iron target, cobalt target, tungsten target, molybdenum target or manganese target.
7. analytical approach according to claim 1, wherein, the condition determination of XRD diffractometer comprises graphite monochromator, the copper target uses power to be 400-3000 watt, the sweep velocity of angular instrument be the 0.01-8.00 degree/minute, sweep limit 2 θ=5 °-160 °, scanning step footpath is 0.010-0.040 degree/step.
8. analytical approach according to claim 7, wherein, the condition determination of XRD diffractometer comprises graphite monochromator, the copper target uses power to be 800-3000 watt, the sweep velocity of angular instrument be the 0.01-4.00 degree/minute, sweep limit 2 θ=10 °-80 °, scanning step footpath is 0.010-0.020 degree/step.
9. analytical approach according to claim 1, wherein, described diffraction peak is the diffraction peak of height intensity, areal intensity or integrated intensity maximum in the diffraction spectrogram.
10. analytical approach according to claim 9, wherein, the intensity of described diffraction peak is the integrated intensity of the diffraction peak of integrated intensity maximum.
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