CN101126733A - Method for evaluating graphite and /or graphitized carbon material electrochemical performance - Google Patents
Method for evaluating graphite and /or graphitized carbon material electrochemical performance Download PDFInfo
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- CN101126733A CN101126733A CNA2006101121742A CN200610112174A CN101126733A CN 101126733 A CN101126733 A CN 101126733A CN A2006101121742 A CNA2006101121742 A CN A2006101121742A CN 200610112174 A CN200610112174 A CN 200610112174A CN 101126733 A CN101126733 A CN 101126733A
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Abstract
The utility model provides an evaluation method of the electrochemical performance of graphite or graphitized carbon material as the cathode material of quadric lithium-ion battery. The method comprises gathering the crystal parameter values of graphite or graphitized carbon material, setting the circumscription of the crystal parameter values of graphite or graphitized carbon material and comparing the gathered crystal parameter values with the preset circumscription of the crystal parameter values. If the gathered crystal parameter values are in the preset circumscription of the crystal parameter values, the electrochemical performance of the graphite or graphitized carbon material meets battery requirement. The crystal parameter values of graphite or graphitized carbon material are the interplanar spacing value and diffraction peak width value or the graphitization degree value and accumulation thickness value of crystal deck and/or size value of crystal. The electrochemical performance is the electrochemical specific volume of the graphite or graphitized carbon material and the cycle life. The method provided by the utility model can judge the electrochemical performance of graphite or graphitized carbon material in short time.
Description
Technical field
The invention relates to the method for a kind of evaluating graphite and/or graphitized carbon material electrochemical performance, especially be used as the mobile phone graphite of secondary lithium battery negative material and/or the method for graphitized carbon material electrochemical performance about a kind of evaluation.
Background technology
Graphite and/or graphitized carbon material have typical layer structure feature, and in the graphite aspect, carbon atom is hexagonal array and extends to two-dimensional directional, and three carbon atoms that each carbon atom is adjacent between aspect are with sp
2There is the structure quite stable in the strong σ bond structure form of hydridization; Between graphite linings and layer, between the carbon-to-carbon only with weak Fan Dehuali (Van der Waals) combination, basal spacing is approximately 0.34 nanometer, because the adhesion weakness between the graphite aspect, and the space is bigger, insert other metals or nonmetal molecule, atom, ion or ionic group easily, form compound between graphite layers (graphite intercalationcompounds is called for short GIC).Therefore, graphite and/or graphitized carbon material are commonly used for the negative electrode active material of secondary lithium battery.
Studies show that, as the quality of mobile phone, very big to the influence of chemical properties such as the capacity of battery, life-span, charge-discharge characteristic with the chemical property of the graphite of secondary lithium battery negative electrode active material and/or graphitized carbon material.Mobile phone with secondary lithium battery manufacturer, is accurately understood and correct the evaluation as the graphite of cell negative electrode material and/or the chemical property of graphitized carbon material, all is considerable to battery design, production and quality control.And the chemical property of thoroughly evaluating graphite and/or graphitized carbon material, common way is according to the production technology of routine graphite and/or graphitized carbon material to be made lithium ion sample battery as negative electrode active material, measure the cycle life of battery then with secondary cell cycle life testing standard, judge according to the cycle life of battery whether the cycle life of graphite and/or graphitized carbon material satisfies the battery needs then; And make positive active material, make button cell as simulated battery as negative electrode active material with lithium metal with tested graphite and/or graphitized carbon material sample, the electrochemistry capacitance of test simulation battery judges in view of the above then whether the electrochemical specific capacity of graphite and/or graphitized carbon material satisfies the battery needs.Judge comprehensively according to above-mentioned cycle life and electrochemical specific capacity whether the chemical property of negative material graphite and/or graphitized carbon material satisfies the battery needs.Though the data that this way obtains are reliably, have the shortcoming that experimental period is long, cost is high.For example,, under the normal condition, need the time of two weeks to 1 month, so Chang experimental period, be difficult to satisfy the Incoming Quality Control demand of battery production producer for cycle life performance test.
Summary of the invention
The objective of the invention is provides the method for a kind of evaluating graphite fast and effeciently and/or graphitized carbon material electrochemical performance in order to overcome existing graphite and/or long shortcoming of graphitized carbon material electrochemical performance evaluation method cycle.
The method of evaluating graphite provided by the invention and/or graphitized carbon material electrochemical performance comprises that (A) obtains graphite and/or graphitized carbon material crystal parameter value; (B) the crystal parameter value scope of setting graphite and/or graphitized carbon material; And (C) judge that graphite and/or graphitized carbon material crystal parameter value are whether in the crystal parameter value scope of setting; When above-mentioned crystal parameter value is in the corresponding crystal parameter value scope of setting, the chemical property of judging this graphite and/or graphitized carbon material satisfies the battery needs, described graphite and/or graphitized carbon material crystal parameter value comprise interplanar distance value and diffraction peak width value or comprise the degree of graphitization value and crystal aspect ulking thickness value and crystal size size value that described chemical property comprises the electrochemical specific capacity and the cycle life of graphite and/or graphitized carbon material.
According to method provided by the invention, only need to start with from the crystal structure of graphite and/or graphitized carbon material, whether the crystal parameter value of judging graphite and/or graphitized carbon material can effectively judge the chemical property of this graphite and/or graphitized carbon material in above-mentioned parameter value scope, thereby can shorten the judgement time whether graphite and/or graphitized carbon material electrochemical performance satisfy the battery needs greatly, this correctly selects starting material to mobile phone for use with secondary lithium battery manufacturer, shorten the supplied materials test verification cycle, reducing the test verification cost all has great importance.And said method only need use XRD diffraction method commonly used once can measure the required graphite of this method and/or graphitized carbon material crystal parameter value (is finished the test of a sample, approximately only need 20 minutes time), thereby simplified operation steps greatly, saved a large amount of man power and materials, thereby production cost is reduced greatly.
The method of evaluating graphite provided by the invention and/or graphitized carbon material electrochemical characteristic be very suitable for mobile phone with secondary lithium battery manufacturer to graphite and/or graphitized carbon material evaluate fast, check and quality control, also be suitable as very much the foundation that graphite and/or graphitized carbon material starting material manufacturer carry out product improvement.
Description of drawings
Fig. 1 is the XRD figure of the graphitized carbon sample that records among the embodiment of the invention 1-6.
Embodiment
According to the present invention, the crystal parameter value of described graphite and/or graphitized carbon material is interplanar distance value and diffraction peak width value.Wherein, described interplanar distance value representation has the graphite of layer structure and/or the distance between the graphitized carbon material aspect.The interplanar distance value is the bridge of contact graphite and/or graphitized carbon material angle of diffraction and structure cell lattice structure, and it is not subjected to the influence of monochromatic x-rays wavelength, promptly no matter the XRD instrument adopts the K of Cu target
αLine is still used the K of Co target
βLine is measured, interplanar distance value to the same crystal face of graphite and/or graphitized carbon material all is the same, but for different types of graphite and/or graphitized carbon material, its crystal structure (unit cell size and shape) varies, the feature interplanar distance value that shows on diffractogram also varies, thus can objective judgement graphite and/or the type of graphitized carbon material.
Distance values between the crystal face that described interplanar distance value can be each crystal face layer, the present invention is preferably the interplanar distance value of 002 crystal face layer (reciprocal lattice) shown in Figure 1, and promptly 002 interplanar distance value is used d
002Expression.d
002Can pass through Bragg equation 2d
002(θ is half of angle of diffraction of XRD determining graphite and/or graphitized carbon material sample diffraction pattern to Sin θ=n λ, λ is the wavelength in the used monochromatic x-rays of instrument source, n is a positive integer, under the certain situation of apparatus measures condition, n λ is a fixed value, unit is a dust) calculate, aforementioned calculation can be finished by the XRD diffractometer.The scope of 002 interplanar distance value of the preferred described setting of the inventor is the 3.35-3.40 dust, more preferably the 3.354-3.370 dust.
According to the present invention, described diffraction peak width value can be the diffraction peak width value of graphite and/or each crystal face of graphitized carbon material crystal, for example can be 002 crystal face shown in Figure 1 and/or the diffraction peak width value of 100 crystal faces.The wide value of integration that described diffraction peak width value can be a diffraction peak also can be the half-peak breadth value of diffraction peak.The preferred described diffraction peak width value of the present invention is that 100 crystal face diffraction peak half-peak breadth values are (to call FWHM in the following text
100) and 002 crystal face diffraction peak half-peak breadth value (to call FWHM in the following text
002).The scope of the half-peak breadth value of 100 crystal face diffraction peaks of described setting is preferably and is no more than 0.520 °, and the scope of the half-peak breadth value of 002 crystal face diffraction peak of described setting preferably is no more than 0.380 °.The half-peak breadth value of crystal face diffraction peak is more little and approach 0 more, the chemical property of graphite and/or graphitized carbon material is good more, but because the cause of instrument, 100 crystal face diffraction peak half-peak breadth value minimums of graphite and/or graphitized carbon material can only reach 0.200 ° at present, the half-peak breadth value minimum of 002 crystal face diffraction peak can only reach 0.100 °, therefore the present invention more preferably the half-peak breadth value of 100 crystal face diffraction peaks be 0.200 °-0.520 °, more preferably 0.100 °-0.380 ° of the half-peak breadth value of 002 crystal face diffraction peak.
According to the present invention, the crystal parameter value of described graphite and/or graphitized carbon material can also be degree of graphitization value, crystal aspect ulking thickness value and/or the crystal size size value of graphite and/or graphitized carbon material, wherein said degree of graphitization value (G%) is in the 0-100% scope, the graphited degree of expression material with carbon element, degree of graphitization is high more, and this material with carbon element is suitable as mobile phone secondary lithium battery negative material more; Degree of graphitization is low more, and this material with carbon element is not suitable for use in mobile phone secondary lithium battery negative material more.According to the present invention, the scope of the degree of graphitization of described setting is 80-100%.Wherein degree of graphitization is lower than 80% material with carbon element and comprises acetylene black, carbon black, and they all are not suitable for use in mobile phone secondary lithium battery negative material.
G% can pass through d
002Calculate: G%=[(3.44-d
002)/(3.44-3.354)] * 100% (d in the formula
002Unit be dust).Work as d
002During=3.354 dusts, degree of graphitization G% is 100%; Work as d
002During=3.44 dusts, degree of graphitization G% is 0%.
Described crystal parameters comprises crystal aspect ulking thickness (representing with Lc) and crystal size size (representing with La).Crystal aspect ulking thickness (Lc) expression graphite and/or graphitized carbon material 002 crystal face are at the axial stack thickness of c.The inventor finds that Lc is big more for crystal aspect ulking thickness, and the discharge capacity of graphite and/or graphitized carbon material is big more.This be because when graphite and/or graphitized carbon material crystal when c direction of principal axis stack thickness big more (being that Lc is big more), the carbon-coating number of plies that can store up lithium is just many more, has correspondingly increased the total amount that can store up lithium ion; In addition, Lc is big more, and " passage " of lithium ion turnover carbon-coating increases, and helps improving the fast charging and discharging ability of graphite and/or graphitized carbon material.For the battery of mobile phone negative material, the crystal aspect ulking thickness Lc of preferred graphite and/or graphitized carbon material is not less than 240 dusts, more preferably the 240-1000 dust.
Lc can calculate by 002 crystal face diffraction peak half-peak breadth value, wherein Lc (dust)=1.54056/ (FWHM
002* Cos θ) (FWHM in the formula
002Unit be radian) or Lc (dust)=(1.54056 * 180)/(FWHM
002* 3.14156 * Cos θ) (FWHM in the formula
002Unit for the degree).
Crystal size size La represents that graphite and/or graphitized carbon material 100 crystal faces are in the axial extension size of a.The inventor finds that crystal size size La is big more, and the stationarity of the low discharging current current potential platform of graphite and/or graphitized carbon material is high more, but the fast charging and discharging ability is low more.When graphite and/or graphitized carbon material crystal when a direction of principal axis extension size big more (being that La is big more), the aspect of graphite and/or graphitized carbon material reaches all the more, the order of stored Li ion is just strong more, the amount that stores the Li ion under the identical situation of other condition just increases, and reversible capacity is just big more; In addition, the order of stored Li ion is just strong more, helps the discharge potential platform of held stationary more.For the battery of mobile phone negative material, the crystal size size of preferred graphite and/or graphitized carbon material is not less than 180 dusts, more preferably the 180-500 dust.
La can calculate by 100 crystal face diffraction peak half-peak breadth values, wherein La (dust)=1.54056/ (FWHM
100* Cos θ) (FWHM in the formula
100Unit be radian) or La (dust)=(1.54056 * 180)/(FWHM
100* 3.14156 * Cos θ) (FWHM in the formula
100Unit for the degree).
The chemical property of graphite of the present invention and/or graphitized carbon material comprises the electrochemical specific capacity and the cycle life of graphite and/or graphitized carbon material.Described electrochemical specific capacity, cycle life are all continued to use the routine definition of this area, for example, described electrochemical specific capacity refers to the size of its electrochemistry capacitance of unit mass material, it is the metric of estimating the battery material electrochemical activity, for secondary cell, generally be meant the reversible electrochemical specific storage, unit is MAH/gram; Described cycle life is meant battery under regular service conditions, and the charge and discharge cycles number of times when battery capacity decays to initial capacity 80%, unit are inferior.This is prerequisite and basis that secondary lithium battery manufacturer designs various different purposes batteries such as battery of mobile phone (need have stable discharge voltage plateau and long discharge time under the low discharging current condition).
When the above-mentioned crystal parameter value of graphite and/or graphitized carbon material was all in corresponding setting range, the chemical property of this graphite and/or graphitized carbon material satisfied the needs of battery.When the needs that the chemical property of graphite of the present invention and/or graphitized carbon material satisfies battery were meant above-mentioned graphite and/or graphitized carbon material made button cell as cell positive material, the electrochemical specific capacity of gained battery was not less than 330 MAH/grams; When above-mentioned graphite and/or graphitized carbon material were made conventional lithium ion battery as cell negative electrode material, cycle life was not less than 400 circulations.
Among the present invention, described graphite and/or graphitized carbon material can be native graphite and/or Delanium, and described Delanium can be soft carbon and/or carbonaceous mesophase spherules.
Among the present invention, described graphite and/or graphitized carbon material crystal parameter value can use the XRD diffraction approach to obtain.Described XRD diffraction approach is that conventional polycrystalline (powder) XRD diffraction approach gets final product, for example can comprise that graphite and/or graphitized carbon material crystal prototype are put into polycrystalline (powder) XRD diffractometer carries out sweep test, x-ray diffractometer is handled according to following order the gained raw data automatically: 9 level and smooth; The button back of the body end; Peak-seeking obtains d
002Value; To d
002Value is carried out correction calculation; Measure the FWHM of 002,100 crystal faces
002, FWHM
100The concrete operations of above-mentioned steps have been conventionally known to one of skill in the art.Record d
002Value, FWHM
002, FWHM
100After, can calculate G%, Lc, La respectively according to above-mentioned formula.
Because general X-ray powder diffraction instrument is generally the light path system of focusing, requirement according to diffraction geometry, institute's specimen should be for having the certain curvature radius (by the radius of turn decision of the angular instrument of instrument, be that specimen surface should bend to that to focus on the curvature in garden consistent with angular instrument), so just can not there be the site error of sample.In fact, because operating aspect, generally, sample is generally flat samples, and tested is a plane, just inevitably has the site error of sample like this at low angle, and this error is a systematic error, is offset to the low angle direction usually.(002) diffraction peak of graphite and/or graphitized carbon material is in low angle of diffraction, and same existence is to the systematic error of low angle skew.Therefore, though not calibrated d
002Value also is available, still, and in order further to improve accuracy, the preferred d that uses after proofreading and correct
002Value.
Proofread and correct graphite and/or graphitized carbon material d
002The method of value can be an internal standard method, promptly in graphite and/or graphitized carbon material powder, add internal standard compound matter (as: silica flour that adds 4 weight %), in test result, utilize the position of the diffraction peak of silica flour to come 002 diffraction peak of graphite and/or graphitized carbon material is proofreaied and correct.The inventor finds, by adopting accurate indexing method to d
002Proofread and correct and to improve d more effectively
002The accuracy of value.Adopt the d of accurate indexing method to graphite and/or graphitized carbon material
002The general step of proofreading and correct is: at first utilize the diffractogram of measuring to find the solution the periodicity and the symmetry (indices of diffraction that are diffraction peak are demarcated) of graphite and/or graphitized carbon material crystal structure, obtain the cell parameter of crystal, further infer point group and the space group that it is possible by systematic extinction law.Then the diffraction peak calibration result is carried out precise treatment correction (being accurate indexing), it is to utilize nonlinear least square to adjust cell parameter and peak shape parameter, make and calculate spectrum best-fit actual measurement spectrum, according to calculating the contrast of spectrum with the actual measurement spectrum, constantly adjust corrected structural model and peak shape parameter, carry out many wheels and calculate, make enough hour of R value index up to calculating the degree that is consistent of spectrum with the actual measurement spectrum, accurate indexing program is finished.Therefore, the present invention is preferably to d
002The method that value is carried out correction calculation is accurate indexing method.Accurate indexing program is generally the self-contained known data processor of a kind of x-ray diffractometer to be provided, for example, just comprise accurate indexing program among the data processor MDI-JADE (5.0) that the D/MAX2200PC type X-ray powder diffraction instrument that Japan company of science produces carries, can be automatically to d
002Value is proofreaied and correct.Unless stated otherwise, d described in the present invention
002Value is meant by gained after the correction of above-mentioned accurate indexing method.
The inventor also finds, causes that the factor of diffraction peak shape broadening mainly contains two classes, the one, and the broadening that equipment factor causes, the 2nd, the broadening that the sample factor causes.So, the present invention preferably when testing with XRD at first the broadening to instrument proofread and correct, comprise the broadening factor eliminating instrument machinery broadening factor (abbreviation instrumental correction) and eliminate X-ray source K α 2 lines (or claim K α line to separate, K α 2 cableties except that).Eliminating the instrument mechanical factor can adopt following method to carry out: adopting granularity is the silica flour (α-SiO of 25-44 micron
2) make standard sample, survey α-SiO with the diffractometer step-scan
2Diffraction peak, the width at this peak is the broadening of instrument own to be caused; Under normal conditions, the broadening function of instrument approaches Gaussian, so sample width commonly used=(test width
2-instrument broadening
2)
1/2Carry out correction calculation.Except the instrument broadening is proofreaied and correct, preferably also adopt the method (Rachinger swarming method) of weighted calculation that K α two-wire is separated, try to achieve the actual width that K α 1 is produced, eliminate the influence of K α 2 lines.Unless stated otherwise, the value of crystal parameter described in the present invention is meant by gained after above-mentioned instrument correction and the parameter correction.The data processor MDI-JADE (5.0) that above-mentioned instrument correction and parameter correction can be carried by the D/MAX2200PC type X-ray powder diffraction instrument that self-contained known program such as the Japan company of science of x-ray diffractometer produces finishes automatically.
The measuring condition of described XRD diffractometer is preferably: the copper X-ray source, and wavelength X=1.54056 dusts, Cu/K α 1, the use power of Cu target are 40 kilovolts, 20 milliamperes; Use graphite monochromator; The sweep speed of angular instrument be 6 the degree/minute, sweep limit 2 θ=10 °-80 °, scan mode is θ/2 θ linked scans; 0.02 degree/the step of footpath scanning step; The light path 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.
Described XRD diffractometer can be various types of polycrystalline (powder) XRD diffractometer, is preferably comprehensive stability and is better than 1% X-ray powder diffraction instrument.Described comprehensive stability can be by duplicate measurements Si standard model under the instrument CONDITIONS IN INELASTIC ELECTRON repeatedly, and for example 10 times, and the relative standard deviation (σ/I) judge for qualified less than 1% of the integrated intensity of the strongest diffraction peak (111 diffraction peak) of calculating Si.
The present invention is further described by the following embodiment.
Present embodiment is used for illustrating the method for evaluating graphite provided by the invention and/or graphitized carbon material electrochemical performance.
Instrument: the D/MAX2200PC type X-ray powder diffraction instrument that Japanese company of science produces;
Instrument configuration and test condition: the copper X-ray source, wavelength X=1.54056 dusts, Cu/K α 1, the use power of Cu target are 40 kilovolts, 20 milliamperes; Use graphite monochromator; The sweep speed of angular instrument be 6 degree/minute, sweep limit is 2 θ=10 °-80 °, scan mode is θ/2 θ linked scans; Scanning step footpath was 0.02 degree/step; The light path 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);
Graphite and/or graphitized carbon material sample: homemade native graphite sample is numbered I;
The concrete operations step:
1, prepares testing sample: get 0.5 gram graphite sample I and 0.3 milliliter of (promptly pipetting 1) silicone oil cementing agent and stir with conventional buret; Getting standard aluminum quality sample framework lies against on the glass planar, test surfaces is downward, in the groove (groove size: 20 millimeters * 18 millimeters * 2 millimeters) of sample framework, fill up the sample I that has stirred, and compacting, remove unnecessary material, carefully pick up aluminium quality sample framework, obtain being parallel to the smooth test surfaces on sample framework surface;
2, prepare instrument: operation D/MAX2200PC type X-ray powder diffraction instrument carries the light path calibration procedure, and the light path system of instrument is adjusted to optimum condition; Duplicate measurements Si standard model 10 times, calculate 111 diffraction peak integrated intensities relative standard deviation (σ/I) less than 1% for qualified;
3, obtain the crystal parameter value: graphite and/or graphitized carbon material powdered sample I are scanned under the condition of setting with X-ray powder diffraction instrument (XRD), obtain the original diffractogram of graphite-powder sample I; X-ray powder diffraction instrument carries out the processing of following order to resultant original diffractogram data automatically: 9 level and smooth; K α 1 separates with K α 2 and revises to eliminate the influence of K α 2; Instrument broadens at correction, the button back of the body end; Peak-seeking; The accurate indexing of diffraction peak; The diffractogram that obtains sample I is shown in the A among Fig. 1; Accurately measure 002 interplanar distance value d
002, 002 and 100 crystal faces half-peak breadth value FWHM
002And FWHM
100The result is as shown in table 1;
4, the chemical property of evaluating graphite sample: with the d of above-mentioned acquisition
002, FWHM
002And FWHM
100Compare with the range of parameter values of corresponding setting provided by the invention, find the d of sample
002, FWHM
002And FWHM
100All in relevant parameters value scope, perhaps according to above-mentioned d
002, FWHM
002And FWHM
100Calculate degree of graphitization G% value, crystal aspect ulking thickness Lc value, crystal size size La value, the result is as shown in table 1, degree of graphitization G% value, crystal aspect ulking thickness Lc value and crystal size size La value with gained compares with the corresponding range of parameter values of setting then, find that G%, Lc and La value are all in the corresponding range of parameter values of setting, the chemical property of judging this graphite thus satisfies the battery needs, is qualified samples.
Embodiment 2-6
Present embodiment 2-6 is used for illustrating the decision method of evaluating graphite provided by the invention and/or graphitized carbon material electrochemical performance.
Graphite shown in the his-and-hers watches 1 and/or graphitized carbon material sample II, III, IV, V and VI carry out the test of XRD diffraction respectively according to embodiment 1 described method of testing, and the chemical property of graphite and/or graphitized carbon material sample is estimated according to embodiment 1 described method, different is that sample I adopts homemade serial graphite and/or graphitized carbon material sample II, III, IV, V and VI to replace respectively, the diffractogram that obtains sample shown in B, C, D, E, F among Fig. 1,002 interplanar distance value d of sample
002, 002 and 100 crystal faces half-peak breadth value FWHM
002And FWHM
100, degree of graphitization G% value, crystal aspect ulking thickness Lc value, crystal size size La value the result as shown in table 1.
Table 1
| The | Embodiment | 1 | |
|
Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Sample number into spectrum | I | II | III | IV | V | VI | |
| Sample type | Native graphite | Native graphite | Native graphite | Native graphite | Soft carbon | Carbonaceous mesophase spherules | |
| d 002(dust) | 3.3699 | 3.3746 | 3.3642 | 3.3636 | 3.3706 | 3.3708 | |
| Degree of graphitization | 81.51％ | 76.04％ | 88.14％ | 93.49％ | 80.70％ | 80.47％ | |
| FWHM 002(°) | 0.311 | 0.324 | 0.335 | 0.219 | 0.474 | 0.387 | |
| FWHM 100(°) | 0.401 | 0.306 | 0.329 | 0.179 | 0.496 | 0.493 | |
| Lc (dust) | 291.59 | 279.86 | 270.67 | 414.08 | 191.28 | 234.30 | |
| La (dust) | 236.00 | 309.29 | 287.68 | 528.78 | 190.81 | 191.99 |
From the result of last table 1 as can be seen, the 002 crystal face diffraction peak basal spacing (d of sample II
002) be worth not in the setup parameter value scope of 3.354-3.370 dust the FWHM of V and two samples of VI
002Value all is not less than 0.380 ° promptly not in the range of parameter values of setting; Perhaps the degree of graphitization G% of sample II is not in the range of parameter values of the setting of 80-100%, crystal aspect ulking thickness (Lc) value of V and two samples of VI is not more than 240 dusts promptly not in the range of parameter values of setting, therefore can judge that the electrochemistry of above-mentioned three samples can satisfy the needs of battery, even also can not reach following requirement simultaneously as the lithium ion battery that cell negative electrode material makes respectively with above-mentioned sample: electrochemical specific capacity is at least 330 MAH/grams, cycle life is at least 400 circulations; 002 crystal face diffraction peak basal spacing (d of I, III, three samples of IV
002) value in the setup parameter value scope of 3.354-3.370 dust, FWHM
002Value is at range of parameter values, FWHM less than 0.380 ° setting
100Value less than the range of parameter values of 0.520 ° setting or degree of graphitization (G) value in the range of parameter values of the setting of 80-100%, crystal aspect ulking thickness (Lc) value is in the range of parameter values greater than the setting of 240 dusts, and crystal size size (La) value is in the range of parameter values greater than the setting of 180 dusts, and therefore judge and use above-mentioned sample to reach following requirement simultaneously as the lithium ion battery that negative electrode active material makes: electrochemical specific capacity is at least 330 MAH/grams, cycle life is at least 400 circulations.
Embodiment 7-12
Following examples are used for verifying the validity of the inventive method.
1, the electrochemical specific capacity of graphite and/or graphitized carbon material.Test the electrochemical specific capacity of graphite and/or graphitized carbon material respectively according to following step:
With thickness is that 0.06 millimeter, diameter are that 16 millimeters, weight are that the metal lithium sheet of 0.0064 gram is a negative electrode active material, is barrier film with the modified polypropene barrier film, with the LiPF of 1 mol
6Solution is electrolytic solution, is positive active material with 0.05 gram and above-mentioned sample I, II, III, graphite or graphitized carbon material that IV, V are identical with VI respectively, makes 2016 type button cell S1-S6.
Respectively according to following step measurements electrochemical specific capacity: battery shelved change into to 0.2 volt of voltage with 0.2 milliampere of electric current after 60 minutes, then respectively with 1 milliampere, 0.8 milliampere, 0.7 milliampere, 0.6 milliampere constant current discharge to 0.005 volt, after shelving 30 minutes, again with 0.5 milliampere, 0.3 milliampere, 0.1 milliampere, 0.06 milliampere, 0.03 milliampere constant current discharge to 0.005 volt, shelve after 30 minutes with 0.3 milliampere of electric current constant current charge, record charges to cell voltage and reaches 2.5 volts time, according to normal capacity (MAH)=charging current (milliampere) * duration of charging of button cell (hour) calculate the normal capacity of button cell, normal capacity promptly gets the electrochemical specific capacity of button cell positive active material (graphite and/or graphitized carbon material) divided by the weight of the positive active material (graphite and/or graphitized carbon material) of button cell, and the result is as shown in table 2.
2, the cycle life of graphite and graphitized carbon material.Test the cycle life of graphite and/or graphitized carbon material respectively according to following step:
With 6.39 gram LiCoO
2Being positive active material, is barrier film with the modified polypropene barrier film, with the LiPF of 1 mol
6Solution is electrolytic solution, is negative electrode active material with 2.84 grams and above-mentioned sample I, II, III, graphite and/or graphitized carbon material that IV, V are identical with VI, makes 043450A type (designing battery capacity is 800 MAHs) secondary lithium battery S1
#-S6
#
Respectively according to the cycle life of following step measurements graphite and/or graphitized carbon material: with 80 milliamperes of (0.1C) constant-current charges 960 minutes, deboost is 4.2 volts, shelved after the charging 15 minutes, with 160 milliamperes of (0.2C) constant current discharge to 3.0 volts, repeat above-mentioned steps, to 80% of initial capacity, write down the number of times of charge and discharge cycles until capacity attenuation, this number of times is the cycle life of secondary cell, and the result is as shown in table 3.
Table 2
| 2016 type button cells numbering | S1 | S2 | S3 | S4 | S5 | S6 |
| The positive active material numbering | I | II | III | IV | V | VI |
| Electrochemical specific capacity (MAH/gram) | 352 | 328 | 364 | 374 | 313 | 321 |
Table 3
| 043450A type secondary lithium battery numbering | S1 # | S2 # | S3 # | S4 # | S5 # | S6 |
| The negative electrode active material numbering | I | II | III | IV | V | VI |
| Cycle life (inferior) | 550 | 400 | 580 | 650 | 395 | 384 |
From the result of table 2 and table 3 as can be seen, the cycle life that adopts the electrochemical specific capacity of the 2016 type button cells that the graphite identical with VI with sample II, V makes to be lower than 330 MAH/grams and/or 043450A type secondary lithium battery respectively is lower than 400 times; The electrochemical specific capacity of the 2016 type button cells made of employing graphite identical with IV with I, III or the graphitized carbon material cycle life that all is higher than 330 MAH/grams and 043450A type secondary lithium battery all is higher than 400 times respectively, the judged result of experimental result and embodiment 1-6 matches, therefore, adopt determination methods provided by the present invention to judge that the chemical property of graphite and/or graphitized carbon material is accurately and reliably.
Claims (5)
1. the method for evaluating graphite and/or graphitized carbon material electrochemical performance is characterized in that this method comprises:
(A) obtain graphite and/or graphitized carbon material crystal parameter value;
(B) the crystal parameter value scope of setting graphite and/or graphitized carbon material; And
(C) judge that graphite and/or graphitized carbon material crystal parameter value are whether in the crystal parameter value scope of setting;
When above-mentioned crystal parameter value is in the corresponding crystal parameter value scope of setting, the chemical property of judging this graphite and/or graphitized carbon material satisfies the battery needs, described graphite and/or graphitized carbon material crystal parameter value are interplanar distance value and diffraction peak width value or are degree of graphitization value, crystal aspect ulking thickness value and/or crystal size size value that described chemical property is the electrochemical specific capacity and the cycle life of graphite and/or graphitized carbon material.
2. method according to claim 1, wherein, the interplanar distance value that described interplanar distance value is 002 crystal face, the interplanar distance value scope of 002 crystal face of described setting is the 3.354-3.370 dust; Described diffraction peak width value comprises the diffraction peak half-peak breadth value of 100 crystal faces and the diffraction peak half-peak breadth value of 002 crystal face, the diffraction peak half-peak breadth value scope of 100 crystal faces of described setting is 0.200 °-0.520 °, and the diffraction peak half-peak breadth value scope of 002 crystal face of setting is 0.100 °-0.380 °.
3. method according to claim 1, wherein, the scope of the degree of graphitization value of described setting is 80-100%, and the scope of the crystal aspect ulking thickness value of described setting is the 240-1000 dust, and the crystal size value scope of described setting is the 180-500 dust.
4. method according to claim 3, wherein, described degree of graphitization value, crystal aspect ulking thickness value and crystal size size value calculate according to interplanar distance value, diffraction peak width value.
5. method according to claim 1, wherein, described graphite and/or graphitized carbon material are native graphite and/or Delanium.
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| CN102236078A (en) * | 2010-04-20 | 2011-11-09 | 深圳市比克电池有限公司 | Method for determining cycle performance of lithium ion battery |
| CN103018301A (en) * | 2012-12-18 | 2013-04-03 | 深圳市金润能源材料有限公司 | Quick test technique for electrochemical performances of carbon anode materials |
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| CN111551572A (en) * | 2020-05-21 | 2020-08-18 | 安徽科达新材料有限公司 | Method for rapidly evaluating cycle performance of graphite material in battery |
| CN115050950A (en) * | 2022-08-12 | 2022-09-13 | 中创新航科技股份有限公司 | Silicon-based negative electrode material, preparation method thereof and lithium ion battery comprising silicon-based negative electrode material |
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| CN102236078A (en) * | 2010-04-20 | 2011-11-09 | 深圳市比克电池有限公司 | Method for determining cycle performance of lithium ion battery |
| CN102236078B (en) * | 2010-04-20 | 2015-05-27 | 深圳市比克电池有限公司 | Method for determining cycle performance of lithium ion battery |
| CN103018301A (en) * | 2012-12-18 | 2013-04-03 | 深圳市金润能源材料有限公司 | Quick test technique for electrochemical performances of carbon anode materials |
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| CN107045106A (en) * | 2016-12-20 | 2017-08-15 | 赣州市瑞富特科技有限公司 | Carbon negative pole material specific capacity and first coulombic efficiency method of testing |
| CN107356877A (en) * | 2017-06-26 | 2017-11-17 | 合肥国轩高科动力能源有限公司 | A kind of method of achievable cycle life of lithium ion battery fast prediction |
| CN109188298A (en) * | 2018-08-21 | 2019-01-11 | 天津力神电池股份有限公司 | A kind of evaluation method of the embedding lithium state of negative electrode of lithium ion battery |
| CN111551572A (en) * | 2020-05-21 | 2020-08-18 | 安徽科达新材料有限公司 | Method for rapidly evaluating cycle performance of graphite material in battery |
| CN115050950A (en) * | 2022-08-12 | 2022-09-13 | 中创新航科技股份有限公司 | Silicon-based negative electrode material, preparation method thereof and lithium ion battery comprising silicon-based negative electrode material |
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