CN100348975C - Quantitative analysis for electrolytic liquor organic component of lithium ion battery - Google Patents
Quantitative analysis for electrolytic liquor organic component of lithium ion battery Download PDFInfo
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- CN100348975C CN100348975C CNB2004100277646A CN200410027764A CN100348975C CN 100348975 C CN100348975 C CN 100348975C CN B2004100277646 A CNB2004100277646 A CN B2004100277646A CN 200410027764 A CN200410027764 A CN 200410027764A CN 100348975 C CN100348975 C CN 100348975C
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 32
- 238000004445 quantitative analysis Methods 0.000 title claims abstract description 16
- 150000002500 ions Chemical class 0.000 claims abstract description 162
- 238000000034 method Methods 0.000 claims abstract description 47
- 238000012360 testing method Methods 0.000 claims abstract description 40
- 238000004458 analytical method Methods 0.000 claims abstract description 27
- 239000003792 electrolyte Substances 0.000 claims abstract description 26
- 238000004364 calculation method Methods 0.000 claims abstract description 8
- 230000003595 spectral effect Effects 0.000 claims abstract description 6
- 238000001819 mass spectrum Methods 0.000 claims abstract description 4
- 230000005477 standard model Effects 0.000 claims description 41
- 230000014759 maintenance of location Effects 0.000 claims description 35
- 238000012544 monitoring process Methods 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 18
- 238000012216 screening Methods 0.000 claims description 14
- 238000012113 quantitative test Methods 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 239000008151 electrolyte solution Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 238000002347 injection Methods 0.000 claims description 9
- 239000007924 injection Substances 0.000 claims description 9
- 238000013459 approach Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 230000010354 integration Effects 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000012159 carrier gas Substances 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 238000004440 column chromatography Methods 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- 239000004615 ingredient Substances 0.000 claims description 3
- 238000011160 research Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 230000004888 barrier function Effects 0.000 claims description 2
- 238000011978 dissolution method Methods 0.000 claims description 2
- 238000010606 normalization Methods 0.000 claims description 2
- 238000002098 selective ion monitoring Methods 0.000 claims 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 13
- 238000004949 mass spectrometry Methods 0.000 description 3
- 239000005486 organic electrolyte Substances 0.000 description 3
- 238000012797 qualification Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 125000005910 alkyl carbonate group Chemical group 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- NPAXBRSUVYCZGM-UHFFFAOYSA-N carbonic acid;propane-1,2-diol Chemical compound OC(O)=O.CC(O)CO NPAXBRSUVYCZGM-UHFFFAOYSA-N 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012956 testing procedure Methods 0.000 description 1
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- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The present invention relates to a quantitative analysis method of organic components in an electrolyte of a lithium ion battery. The method comprises the following steps: (1) preparing a sample to be tested; (2) preparing a standard sample, and obtaining the mass percentage value P<ib> of each organic component; (3) carrying out qualitative spectral scanning analysis to the exact mass percentage value of each known organic component of the standard sample by a gas chromatogram-mass spectrum combining instrument to obtain the mass-to-charge ratio (m/z) value M<im> of the target ions of each organic component and the mass-to-charge ratio (m/z) value M<it> of characteristic ions; (4) testing and analyzing the standard sample by a selective ion method to obtain the integrated intensity value Q<imb> of the target ions of each organic component of the standard sample; (5) testing and analyzing the sample to be tested by the selective ion method to obtain the integrated intensity value Q<imd> of the target ions of each organic component in the sample to be tested; (6) inputting the percentage value p<ib> obtained in step (2), the integrated intensity value Q<imb> obtained in step (4) and the integrated intensity value Q<imd> obtained in step (5) into calculation formulas of P<d>=*P<ib>*Q<imd>/Q<imb> and P<id>=(p<ib>*Q<imd>)/(P<d>*Q<imb>)*100%, and calculating the mass percentage value P<id> of each component of the sample to be tested by calculating the ratio of the integrated intensity of the target ions of each component of the sample to be tested and the standard sample and utilizing a mathematic normalizing method.
Description
Technical field
What the present invention relates to is the quantitative analysis method of each organic component of battery electrolyte, especially a kind of quantitative analysis method of lithium-ion battery electrolytes organic component.
Background technology
Lithium-ion battery electrolytes is very responsive to performances such as the energy density of electrode and battery, cycle life, securities.Conductivity, the battery that Chen Dejun has summarized lithium ion battery organic electrolyte commonly used the 149th～153 page of " battery industry " periodical 1999 the 4th (4) phase learned the general requirement to electrolytic solution of performance such as stability and battery.Wear the Quannan and rolled up the 6th～12 page of latest developments of reporting lithium-ion battery electrolytes at 1996 the 11st at " the 22nd physical power source nd Annual Meeting collection of China ".For lithium ion battery, selecting suitable organic electrolyte is one of key issue that obtains high-energy-density, long circulation life and cell safety.The initial charge/discharge capacity of battery has sizable difference owing to the combination of material with carbon element and electrolytic solution is different, so lay special stress on electrolytic solution will adapt with carbon anode when the design battery.In the commodity lithium ion battery, the most frequently used lithium salts of electrolytic solution is LiPF
6, solvent is that cyclic carbonate Arrcostab (EC, PC etc.) and chain alkyl carbonate (DEC, DMC, DME and EMC) mix, and is binary, ternary or multicomponent system that main body is formed with EC.Organic electrolyte plays a part to carry lithium ion between the both positive and negative polarity of lithium ion battery, although can form electrolytic solution by a variety of organic solvents and lithium salts, that really can use in lithium ion battery is few in number.Because separate liquid and must satisfy some specific performance properties requirements should having access to electricity.
The organic component of lithium-ion battery electrolytes mainly contains:
Dimethyl carbonate (CH
3O)
2CO Dimethyl Carbonate DMC
Diethyl carbonate (C
2H
5O)
2CO Diethyl Carbonate DEC
Ethylene carbonate ester C
3H
4O
3Ethylene Carbonate EC
Propylene glycol carbonate C
4H
6O
3Propylene Carbonate PC
Methyl ethyl carbonate (C
2H
5O) CO (OCH
3) Ethyl Methyl Carbonate EMC
Bradley A.Johnson and Ralph E.White utilize GC/MS to analyze the lithium ion battery organic electrolyte in the 48th～54 page of proposition of J.of Power Sour. periodical the 70th volume in 1998, and they have collected Sony, Sanyo Electric, Matsushita Electric Industrial, Moli Energy and A﹠amp; 85 lithium ion batteries of T Battery five companies are analyzed, and except the lithium ion battery of MatsushitaElectric Industrial is 17500 types, other is 18650 types.Article utilizes gas chromatograph-mass spectrometer (GCMS) (GC/MS) only each component of lithium ion battery organic electrolyte to be carried out qualitative analysis, analysis result such as following table:
| Production company | Form | ||||
| EC | PC | DMC | DEC | EMC | |
| Sony | Do not detect | Have | Have | Do not detect | Have |
| Moli | Have | Do not detect | Do not detect | Have | Do not detect |
| A&T | Have | Do not detect | Do not detect | Do not detect | Have |
| Sanyo | Have | Do not detect | Have | Have | Do not detect |
| Matsushita | (not detecting) | Do not detect | Have | Have | Have |
Quantitative test is not done in this experiment, but confirmed substantially except the Sony electrolyte system be principal ingredient (its negative material is coke Coke) with PC, the electrolyte system of other company is principal ingredient (its negative material is graphite Graphite) with EC.The percent by volume of each component of the lithium ion battery organic electrolyte of each company all meets the matching principle of maximum conductivity approx, referring to following document:
1、M.Ishikawa，M.Morita，M.Asao and Y. Matsuda，J.Electrochem.Soc.，141(1994)1105-1108
2、M.Terasaki，H.Yoshida，H.Tukamoto，M.Mizutani and M.Yamachi，Denki kagaku，61(1993)1417-1418
3、J.T.Dudley，D.P.Wilkinson，G. Thomas，R.LeVae，S.Woo，H.Blom，C.Horvath，M.W. Juzkow，35(1991)59-82
Mass percent by available each component of lithium ion battery organic electrolyte of this matching principle preparation is semiquantitative data, is 3: 1: 2 as EMC, DEC, three kinds of set of dispense ratios of EC.
Steven E.Sloop, John B.Kerr and Kim Kinoshita use GC/MS (Agilent6890/5973 MSD) that lithium-ion battery electrolytes organic component DMC, EMC, DEC and the EC etc. of methylene chloride dissolving have been carried out qualitative analysis in J.of PowerSour. periodical 119-121 in 2003 rolls up the 330th～337 page article, also do not carry out quantitative test.
Summary of the invention
The purpose of this invention is to provide a kind of gas chromatograph-mass spectrometer (GCMS) that utilizes and select the quantitative analysis method of ion method the lithium-ion battery electrolytes organic component.
The quantitative analysis method of lithium-ion battery electrolytes organic component of the present invention may further comprise the steps:
1), testing sample preparation: after adopting the organic solvent dissolution method that electrolytic solution is carried out pre-service, obtain testing sample;
2), standard model preparation: adopt analytical balance weighing method preparation standard sample, and obtain each organic component mass percent numerical value p
Ib(i=1,2 ..., n, n are organic component number in the sample);
3), utilize gas chromatograph-mass spectrometer (GCMS) that known each the organic component quality of standard model is carried out the qualitative spectral scan analysis than exact value, employed object ion and characteristic ion in screening and the definite quantitative test, and obtain the mass-to-charge ratio m/z value M of each organic component object ion
Im(i=1,2 ..., n, n are organic component number in the sample) and the mass-to-charge ratio m/z value M of characteristic ion
It(i=1,2 ..., n, n are organic component number in the sample);
4), according to the mass-to-charge ratio m/z value M of the object ion of each selected component of step 3)
ImMass-to-charge ratio m/z value M with characteristic ion
It, carry out test analysis with selecting ion method that standard model is set, obtain the integrated intensity value Q of each organic component object ion of standard model
Imb(i=1,2 ..., n, n are organic component number in the sample);
5), according to the step 3) mass-to-charge ratio m/z value M of the object ion of each selected component
ImMass-to-charge ratio m/z value M with characteristic ion
It, carry out test analysis with selecting ion method that testing sample is set, obtain the integrated intensity value Q of each organic component object ion in the testing sample
Imd(i=1,2 ..., n, n are organic component number in the sample);
6), with step 2) middle each percentages of ingredients numerical value p of standard model
IbThe integrated intensity value Q of each organic component object ion of standard model in the step 4)
ImbThe integrated intensity value Q of each organic component object ion in the testing sample in the step 5)
ImdIn the input computing formula, by ratio that calculates testing sample and the object ion integrated intensity of each organic component of standard model and the mass percent numerical value p that utilizes each component of mathematics method for normalizing calculating testing sample
Id(i=1,2 ..., n, n are organic component number in the sample), computing formula is as follows:
p
id＝(p
ib×Q
imd)/(P
d×Q
imb)×100％
Wherein, i=1,2 ..., n, n are organic component number in the sample
Preprocess method for the lithium-ion battery electrolytes of dissecting in the described testing sample preparation is that chromatographically pure organic solvent 3～8mL is injected the battery case that has taken out both positive and negative polarity and barrier film, slight vibration 3～5 times, leave standstill 20～30min, getting wherein, 1～2mL is transferred in the 2mL sample bottle; Step 1 is to get electrolytic solution 2～10 μ L with the injection sampler to inject the 2mL sample bottle that 1～2mL chromatographically pure organic solvent has been housed for the preprocess method without the lithium-ion battery electrolytes that uses, and vibrates 3～5 times, leaves standstill 10～20min.
Described organic solvent can be acetone, isopropyl alcohol, ethanol, methylene chloride.
The analytical balance weighing method comprises in the described standard model preparation:
The mass ratio of each organic component in A, the estimation testing sample, and with the reference standard of this mass ratio as the mass ratio of each organic component in the standard model of preparation;
B, be the mass value of 30～50 each organic component of gram basis of calculation sample according to the gross mass M of standard model of preparation;
C, get one of the clean small beaker of 100ml, utilize the accurate weighing mass value of analytical balance to be m
0
D, in beaker, add each organic component successively, and write down the gross mass value m that adds the back beaker respectively according to each organic component volatile grade order from small to large
i(i=1,2 ..., n, n are organic component number in the sample), in the interpolation process, should guarantee each mass value m that adds
i-m
I-1(i=1,2 ..., n, n are organic component number in the sample) respectively as far as possible near front institute result calculated;
E, envelope beaker mouth utilize the magneton stirrer to stir 30～40min, leave standstill 10～20min, get this mixed liquor 2～10 μ L with the injection sampler then and inject the 2mL sample bottle that 1～2mL chromatographically pure acetone reagent has been housed, vibrate 3～5 times, leave standstill 10～20min, to be measured, be standard model.The mass ratio of each organic component of standard model is known m
i-m
I-1Quality ratio, for simple and Convenient Calculation can represent to be that normalization is represented with percentages with it:
p
Ib=(m
i-m
I-1)/(m
i-m
0) * 100% (i=1,2 ..., n, n are organic component number in the sample)
Described screening and definite object ion and characteristic ion may further comprise the steps:
A, utilize gas chromatograph-mass spectrometer (GCMS) that known each organic component quality is carried out the qualitative spectral scan analysis than the standard model of exact value, setting solvent time delay is 2.10～2.90min in this analytical approach, sample size 0.2～2.0 μ L, the injection port split ratio is 5: 1～20: 1, researchs and analyses the retention time of each the organic component chromatographic peak among the result and the retention time scope that factors such as width and shape are also determined the analytical test of each organic component thus thereof;
B, according to the screening scope of who high principle select target ion, in the pairing mass spectrogram of peak value retention time of the chromatographic peak of component to be measured, obtain the mass-to-charge ratio m/z value of the ion to be selected of 5 object ions; Select the screening scope of characteristic ion according to the singularity principle, select the ion that has feature mass-to-charge ratio m/z value most, in the pairing mass spectrogram of peak value retention time of the chromatographic peak of component to be measured, obtain the mass-to-charge ratio m/z value of the ion to be selected of 5 characteristic ions;
The selection analytical approach of C, target setting ion and characteristic ion is utilized all ions to be selected in the screening scope of SIM mode monitoring standard sample, obtains a standard model ion flow collection of illustrative plates to be selected;
In D, the standard model ion flow collection of illustrative plates to be selected, the mass spectra peak intensity of each ion to be selected of each component is carried out integration to be added and calculates, add should be in full accord with the method for areal intensity for the integration that ion to be selected adopted of every group of close alternative in calculating, calculates the integrated intensity of all ions to be selected;
E, in every group of 5 ions to be selected, selected integrated intensity soprano is an employed ion in the final quantitative test; If the two integrated intensity value of integrated intensity soprano and integrated intensity differed less than 5% o'clock, should consider the influence of the integrated intensity of the ion to be selected before and after this two, should select position in the two at last and be employed ion in the final quantitative test near of integrated intensity third; If the integrated intensity value of integrated intensity third and integrated intensity fourth differed also less than 5% o'clock, still select the integrated intensity soprano to be employed ion in the final quantitative test.
The capillary column chromatography condition determination is in the described selection ion method: chromatographic column is a quartz capillary column, column length 25～40m, internal diameter 0.25～0.50mm, thick 0.25～0.50 μ m of internal coating, the internal coating material is 5%-diphenyl-95%-dimethylsiloxane copolymer; Column temperature is heating schedule control, 30～60 ℃ of initial temperatures, and constant temperature time 1.00～2.50min is warming up to 140～180 ℃ with 5～15 ℃/min speed, constant temperature 8～1 5min; 240～300 ℃ of injector temperatures; Carrier gas is high-purity He, and pressure is 68.0～90.0KPa, total flow 9.0～15.0mL/min, and split ratio is 5: 1～20: 1.
In the quantitative analysis method of lithium-ion battery electrolytes organic component of the present invention the mass ratio of each organic component of lithium-ion battery electrolytes is measured, quantitative test simultaneously common adjuvant VC, the GHP of lithium-ion battery electrolytes, the mass ratio of BP, this is the work of not doing in the above-mentioned document.
VC, English name 1,3-dioxol-2-one, molecular formula C
3H
2O
3, molecular weight 86;
GHP, English name cyclohexyl benzene, molecular formula C
12H
16, molecular weight 160;
BP, English name biphenyl, molecular formula C
12H
10, molecular weight 154.
The quantitative analysis method of lithium-ion battery electrolytes organic component of the present invention, under the normal operation and maintenance of instrument, the object ion and the characteristic ion of each organic component in certain period in (in six months) lithium-ion battery electrolytes can not change, so the selection of object ion and characteristic ion is carried out 1 time get final product every half a year.When test analysis sample at ordinary times, as long as carry out one, five, six in the top described determination step, simplify testing procedure like this, saved analysis time, improved analysis efficiency, thereby realized measuring the target quick, simple to operate, that accuracy is high.
The concrete grammar of the quantitative analysis method of lithium-ion battery electrolytes organic component of the present invention is provided in detail by following examples.
Embodiment
Embodiment: the instrument of use: HP6890 gas chromatograph, HP5973 mass detector; Adopting organic solvent is acetone reagent: German Merck company produces chromatographically pure.
Standard model has 7 kinds of organic component: BP, GHP, EC, DEC, VC, EMC, DMC, i.e. i=1,2 ..., 7.
Determination step:
1), the preparation of testing sample, adopt the acetone solution method: to the preprocess method without the lithium-ion battery electrolytes that uses is to get electrolytic solution 10 μ L with the injection sampler to inject the 2mL sample bottle that 1mL chromatographically pure acetone reagent has been housed, vibrate 5 times, leave standstill 20min, to be measured.
2), the preparation of standard model, adopt analytical balance weighing method: A, estimate the mass ratio of each organic component in the testing sample, and with the reference standard of this mass ratio as the mass ratio of each organic component in the standard model of preparation; B, be the mass value of 40 each organic component of gram basis of calculation sample according to the gross mass M of standard model of preparation; C, get one of the clean small beaker of 100ml, utilize the accurate weighing mass value of analytical balance to be m
0D, in beaker, add BP, GHP, EC, DEC, VC, EMC, DMC successively, and write down the gross mass value m that adds the back beaker respectively according to each organic component volatile grade order from small to large
1, m
2, m
3, m
4, m
5, m
6, m
7, in the interpolation process, should guarantee (m
1-m
0), (m
2-m
1), (m
3-m
2), (m
4-m
3), (m
5-m
4), (m
6-m
5), (m
7-m
6) mass value respectively as far as possible near front institute result calculated; E, sealed beaker mouth utilize the magneton stirrer to stir 40min, leave standstill 20min, get this mixed liquor 10 μ L with the injection sampler then and inject the 2mL sample bottle that 1mL chromatographically pure acetone reagent has been housed, vibrate 5 times, leave standstill 20min, and be to be measured, is standard model.The mass ratio of each organic component of standard model is known (m
1-m
0), (m
2-m
1), (m
3-m
2), (m
4-m
3), (m
5-m
4), (m
6-m
5), (m
7-m
6) quality ratio, for simple and Convenient Calculation can promptly be expressed as follows the row formula with percentages with its mathematics normalized:
p
ib＝(m
i-m
i-1)/(m
i-m
0)×100％
Analytical balance measurement data such as table 1, each organic component mass percent numerical value p
bResult of calculation such as table 2.
Table 1
| The measurement project | m 0 | m 1 | m 2 | m 3 | m 4 | m 5 | m 6 | m 7 |
| Quality (gram) | 48.4735 | 53.1801 | 68.7172 | 68.9758 | 74.1664 | 84.6766 | 86.3021 | 87.8586 |
Table 2
| Component | DMC | EMC | VC | DEC | EC | GHP | BP |
| Mass percent p ib | p 7b | p 6b | p 5b | p 4b | p 3b | p 2b | p 1b |
| 11.9502 ％ | 39.4492 ％ | 0.6566 ％ | 13.1791 ％ | 26.6857 ％ | 4.1272 ％ | 3.9520 ％ |
3), employed object ion and characteristic ion in screening and the definite quantitative test:
A, utilize gas chromatograph-mass spectrometer (GCMS) that known each organic component quality is carried out the qualitative spectral scan analysis than the standard model of exact value, setting solvent time delay is 2.10min in this analytical approach, sample size 1.0 μ L, the injection port split ratio is 10: 1, researchs and analyses the retention time of each the organic component chromatographic peak among the result and the retention time scope that factors such as width and shape are also determined the analytical test of each organic component thus thereof.Capillary column chromatography condition determination in the analysis: chromatogram column length 30m, internal diameter 0.25mm, the thick 0.25 μ m of internal coating, the internal coating material is 5%-diphenyl-95%-dimethylsiloxane copolymer, quartz capillary column; Column temperature is heating schedule control, 45 ℃ of initial temperatures, and constant temperature 1.50min is warming up to 150 ℃ with 10 ℃/min speed, constant temperature 12min; 280 ℃ of injector temperatures; Carrier gas is high-purity He, and pressure is 82.0KPa, total flow 12.4mL/min, and split ratio is 10: 1.Mass spectroscopy condition: EI ion gun, electron energy 70eV, 230 ℃ of ion source temperatures, 150 ℃ of quadrupole rod temperature, 280 ℃ of interface temperature, electron-multiplier voltage 2100V, the full spectrum scanning in ion detection mass-to-charge ratio m/z=20.0～300.0.In full spectrum scanning spectra, determine the retention time of each organic component successively, and take all factors into consideration the retention time parameter of determining after the factors such as width, shape at the corresponding peak of this component institute in the selection ion method analysis of back, see Table 3:
Table 3
| Component | The retention time scope (minute) | |
| DMC | t 7～t 6 | 2.10～2.75min |
| EMC | t 6～t 5 | 2.75～3.35min |
| VC | t 5～t 4 | 3.35～3.73min |
| DEC | t 4～t 3 | 3.73～6.50min |
| EC | t 3～t 2 | 6.50～13.5min |
| GHP | t 2～t 1 | 13.5～14.9min |
| BP | t 1～t 0 | 14.9～20.0min |
B, determine the scope of ion to be selected, who high principle at first to select the screening scope of each organic component object ion according to: in the pairing mass spectrogram of peak value retention time of the chromatographic peak of component to be measured, the ion of selection maximum intensity is write down the mass-to-charge ratio m/z value of this ion, be accurate to 0.1 order of magnitude, then on this numerical value respectively-0.2 ,-0.1 ,+0.0 ,+0.1 ,+0.2, obtain the mass-to-charge ratio m/z value of 5 numerical value as the ion to be selected of object ion; Select the screening scope of each organic component characteristic ion then according to the singularity principle: in the pairing mass spectrogram of peak value retention time of the chromatographic peak of component to be measured, select to have the ion of feature mass-to-charge ratio m/z value most and require the absolute strength of this ion to be not less than 10% of pairing object ion absolute strength, write down the mass-to-charge ratio m/z value of this ion, be accurate to 0.1 order of magnitude, then on this numerical value respectively-0.2 ,-0.1 ,+0.0 ,+0.1 ,+0.2, obtain the mass-to-charge ratio m/z value of 5 numerical value as the ion to be selected of characteristic ion.
The selection analytical approach of C, target setting ion and characteristic ion, utilize all ions to be selected in the screening scope of SIM detection mode each organic component object ion of the correspondence in the monitoring standard sample and characteristic ion in the retention time scope of each organic component, obtain a standard model ion flow collection of illustrative plates to be selected.
D, in standard model ion flow collection of illustrative plates to be selected, the mass spectra peak intensity of each ion to be selected of each component is carried out integration to be added and calculates, add should be in full accord with the method for areal intensity for the integration that ion to be selected adopted of every group of close alternative in calculating, calculates the integrated intensity of all ions to be selected.
E, in every group of 5 ions to be selected, selected integrated intensity soprano is an employed ion in the final quantitative test; If the two integrated intensity value of integrated intensity soprano and integrated intensity differed less than 5% o'clock, should consider the influence of the integrated intensity of the ion to be selected before and after this two, should select position in the two at last and be employed ion in the final quantitative test near of integrated intensity third; If the integrated intensity value of integrated intensity third and integrated intensity fourth differed also less than 5% o'clock, still select the integrated intensity soprano to be employed ion in the final quantitative test.
The mass-to-charge ratio m/z value M of the object ion that each organic component is selected
ImMass-to-charge ratio m/z value M with each organic component characteristic ion
ItAs table 4.
Table 4
| Component | DMC | EMC | VC | DEC | EC | GHP | BP |
| Object ion mass-to-charge ratio M im | M 7m | M 6m | M 5m | M 4m | M 3m | M 2m | M 1m |
| 59.0 | 77.0 | 86.0 | 91.0 | 88.0 | 160.1 | 154.1 |
| Characteristic ion mass-to-charge ratio M it | M 7t | M 6t | M 5t | M 4t | M 3t | M 2t | M 1t |
| 90.0 | 45.0 | 29.0 | 45.0 | 29.0 | 104.0 | 76.0 |
4), according to the object ion of each selected component of step 3 and characteristic ion standard model is set and to be carried out test analysis, analytical approach is for selecting ion method.Capillary column chromatography condition determination in the analysis: chromatogram column length 30m, internal diameter 0.25mm, the thick 0.25 μ m of internal coating, the internal coating material is 5%-diphenyl-95%-dimethylsiloxane copolymer, quartz capillary column; Column temperature is heating schedule control, 45 ℃ of initial temperatures, and constant temperature 1.50min is warming up to 150 ℃ with 10 ℃/min speed, constant temperature 12min; 280 ℃ of injector temperatures; Carrier gas is high-purity He, and pressure is 82.0KPa, total flow 12.4mL/min, and split ratio is 10: 1; The mass spectroscopy condition: the EI ion gun, electron energy 70eV, 230 ℃ of ion source temperatures, 150 ℃ of quadrupole rod temperature, 280 ℃ of interface temperature, electron-multiplier voltage 2100V, set ion monitoring mass-to-charge ratio m/z value in corresponding retention time:
At t
7～t
6Monitoring mass-to-charge ratio m/z value is M in the retention time
7mAnd M
7tIon
At t
6～t
5Monitoring mass-to-charge ratio m/z value is M in the retention time
6mAnd M
6tIon
At t
5～t
4Monitoring mass-to-charge ratio m/z value is M in the retention time
5mAnd M
5tIon
At t
4～t
3Monitoring mass-to-charge ratio m/z value is M in the retention time
4mAnd M
4tIon
At t
3～t
2Monitoring mass-to-charge ratio m/z value is M in the retention time
3mAnd M
3tIon
At t
2～t
1Monitoring mass-to-charge ratio m/z value is M in the retention time
2mAnd M
2tIon
At t
1～t
0Monitoring mass-to-charge ratio m/z value is M in the retention time
1mAnd M
1tIon
The object ion integrated intensity Q of each organic component in can getting standard samples by test analysis
ImbWith characteristic ion integrated intensity Q
Itb, see Table 5.
Table 5
| Component | Object ion M im | Object ion integrated intensity value | Characteristic ion M it | Characteristic ion integrated intensity value | ||
| DMC | M 7m | Q 7mb | 2391070.400 | M 7t | Q 7tb | 289319.518 |
| EMC | M 6m | Q 6mb | 5633744.125 | M 6t | Q 6tb | 5605575.404 |
| VC | M 5m | Q 5mb | 300371.750 | M 5t | Q 5tb | 108734.574 |
| DEC | M 4m | Q 4mb | 2784876.839 | M 4t | Q 4tb | 3113492.306 |
| EC | M 3m | Q 3mb | 3935522.292 | M 3t | Q 3tb | 4722626.750 |
| GHP | M 2m | Q 2mb | 2263323.250 | M 2t | Q 2tb | 2906107.053 |
| BP | M 1m | Q 1mb | 6183473.993 | M 1t | Q 1tb | 816218.567 |
With Q in the table 5
ItbAnd Q
ImbData are calculated by following formula, and the characteristic ion of each organic component that can get standard samples is to the qualifications of object ion, the i.e. ratio I of the intensity of the intensity of characteristic ion and object ion
Ib, see Table 6.
I
ib＝Q
itb/Q
imb×100％
Table 6
| Component | DMC | EMC | VC | DEC | EC | GHP | BP |
| The ratio I of the intensity of characteristic ion and the intensity of object ion ib(％) | I 7b | I 6b | I 5b | I 4b | I 3b | I 2b | I 1b |
| 12.1 | 99.5 | 36.2 | 111.8 | 120.0 | 128.4 | 13.2 |
5), according to the object ion of each selected component of step 3) and characteristic ion testing sample is set and to be carried out test analysis, analytical approach is for selecting ion method.Capillary column chromatography condition determination in the analysis: chromatogram column length 30m, internal diameter 0.25mm, the thick 0.25 μ m of internal coating, the internal coating material is 5%-diphenyl-95%-dimethylsiloxane copolymer, quartz capillary column; Column temperature is heating schedule control, 45 ℃ of initial temperatures, and constant temperature 1.50min is warming up to 150 ℃ with 10 ℃/min speed, constant temperature 12min; 280 ℃ of injector temperatures; Carrier gas is high-purity He, and pressure is 82.0KPa, total flow 12.4mL/min, and split ratio is 10: 1; The mass spectroscopy condition: the EI ion gun, electron energy 70eV, 230 ℃ of ion source temperatures, 150 ℃ of quadrupole rod temperature, 280 ℃ of interface temperature, electron-multiplier voltage 2100V, set ion monitoring mass-to-charge ratio m/z value in corresponding retention time:
At t
7～t
6Monitoring mass-to-charge ratio m/z value is M in the retention time
7mAnd M
7tIon
At t
6～t
5Monitoring mass-to-charge ratio m/z value is M in the retention time
6mAnd M
6tIon
At t
5～t
4Monitoring mass-to-charge ratio m/z value is M in the retention time
5mAnd M
5tIon
At t
4～t
3Monitoring mass-to-charge ratio m/z value is M in the retention time
4mAnd M
4tIon
At t
3～t
2Monitoring mass-to-charge ratio m/z value is M in the retention time
3mAnd M
3tIon
At t
2～t
1Monitoring mass-to-charge ratio m/z value is M in the retention time
2mAnd M
2tIon
At t
1～t
0Monitoring mass-to-charge ratio m/z value is M in the retention time
1mAnd M
1tIon
The pairing peak of the limit standard and the peak value retention time of object ion being determined each organic component in the testing sample according to the characteristic ion of each organic component.Limit standard is as follows: (I
7d, I
6d, I
5d, I
4d, I
3d, I
2d, I
1dBe respectively testing sample t
7～t
6, t
6～t
5, t
5～t
4, t
4～t
3, t
3～t
2, t
2～t
1, t
1～t
0The ratio of the intensity of the intensity of the characteristic ion at each peak and object ion in the retention time.)
According to the I of step 4) by table 7
IbThe result can calculate the ratio I of the intensity of the intensity of testing sample characteristic ion and object ion
IdSpan, as table 7:
Table 7
| I id | Qualifications | Span |
| I 7d | I 7b×0.8＜I 7d＜I 7b×1.2 | 9.7％～14.5％ |
| I 6d | I 6b×0.8＜I 6d＜I 6b×1.2 | 79.6％～119.4％ |
| I 5d | I 5b×0.8＜I 5d＜I 5b×1.2 | 29.0％～43.4％ |
| I 4d | I 4b×0.8＜I 4d＜I 4b×1.2 | 89.4％～134.2％ |
| I 3d | I 3b×0.8＜I 3d＜I 3b×1.2 | 96.0％～144.0％ |
| I 2d | I 2b×0.8＜I 2d＜I 2b×1.2 | 102.7％～154.1％ |
| I 1d | I 1b×0.8＜I 1d＜I 1b×1.2 | 10.6％～15.8％ |
In each retention time section, has 1 or do not have qualified peak, if not then show in the testing sample not this component.
Can obtain the integrated intensity value Q of the object ion of each organic component in the testing sample by test analysis
Imd: (if there is not qualified peak in the qualifications in front, the object ion integrated intensity that then defines this component is 0.) data recording such as table 8.
Table 8
| Component | Object ion | Object ion integrated intensity value | |
| DMC | M 7m | Q 7md | 4325233.258 |
| EMC | M 6m | Q 6md | 4799208.627 |
| VC | M 5m | Q 5md | 0 |
| DEC | M 4m | Q 4md | 37518.435 |
| EC | M 3m | Q 3md | 5987663.362 |
| GHP | M 2m | Q 2md | 1808285.722 |
| BP | M 1m | Q 1md | 16330402.016 |
6), utilize the mathematics method for normalizing, with step 2) middle each percentages of ingredients numerical value p of standard model
IbIntegrated intensity value Q with each organic component object ion of standard model in the step 4)
ImbIntegrated intensity value Q with each organic component object ion in the testing sample in the step 5)
ImdImport in the following computing formula, obtain P
d:
P
d＝p
7b×Q
7md/Q
7mb+p
6b×Q
6md/Q
6mb+p
5b×Q
5md/Q
5mb+p
4b×Q
4md/Q
4mb+p
3b×Q
3md/Q
3mb+p
2b×Q
2md/Q
2mb+p
1b×Q
1md/Q
1mb＝109.7352％
With P
dFormula below the substitution calculates the mass ratio p of each component of testing sample
Id, as table 9.
p
id＝(p
ib×Q
imd)/(P
d×Q
imb)×100％
Table 9
| Component | DMC | EMC | VC | DEC | EC | GHP | BP |
| p id | p 7d | p 6d | p 5d | p 4d | p 3d | p 2d | p 1d |
| Mass ratio | 19.6991 ％ | 30.6242 ％ | Do not detect | 0.1618 ％ | 36.9988 ％ | 3.0049 ％ | 9.5112 ％ |
Claims (6)
1, a kind of quantitative analysis method of lithium-ion battery electrolytes organic component may further comprise the steps:
1), testing sample preparation: after adopting the organic solvent dissolution method that electrolytic solution is carried out pre-service, obtain testing sample;
2), standard model preparation: adopt analytical balance weighing method preparation standard sample, and obtain each organic component mass percent numerical value p
Ib(i=1,2 ..., n, n are organic component number in the sample);
3), utilize gas chromatograph-mass spectrometer (GCMS) that known each the organic component quality of standard model is carried out the qualitative spectral scan analysis than exact value, employed object ion and characteristic ion in screening and the definite quantitative test, and obtain the mass-to-charge ratio m/z value M of each organic component object ion
Im(i=1,2 ..., n, n are organic component number in the sample) and the mass-to-charge ratio m/z value M of characteristic ion
It(i=1,2..., n, n are organic component number in the sample);
4), according to the mass-to-charge ratio m/z value M of the object ion of each selected component of step 3)
ImMass-to-charge ratio m/z value M with characteristic ion
It, carry out test analysis with selecting ion method that standard model is set, obtain the integrated intensity value Q of each organic component object ion of standard model
Imb(i=1,2 ..., n, n are organic component number in the sample);
5), according to the step 3) mass-to-charge ratio m/z value M of the object ion of each selected component
ImMass-to-charge ratio m/z value M with characteristic ion
It, carry out test analysis with selecting ion method that testing sample is set, obtain the integrated intensity value Q of each organic component object ion in the testing sample
Imd(i=1,2 ..., n, n are organic component number in the sample);
6), with step 2) middle each percentages of ingredients numerical value P of standard model
IbThe integrated intensity value Q of each organic component object ion of standard model in the step 4)
ImbThe integrated intensity value Q of each organic component object ion in the testing sample in the step 5)
ImdIn the input computing formula, by ratio that calculates testing sample and the object ion integrated intensity of each organic component of standard model and the mass percent numerical value pid (i=1 that utilizes each organic component of mathematics method for normalizing calculating testing sample, 2, ..., n, n is an organic component number in the sample), computing formula is as follows:
p
id＝(p
ib×Q
imd)/(P
d×Q
imb)×100％
Wherein, i=1,2 ..., n, n are organic component number in the sample.
2, the quantitative analysis method of a kind of lithium-ion battery electrolytes organic component according to claim 1, it is characterized in that: in the step 1 testing sample preparation for the lithium-ion battery electrolytes of dissecting, be that chromatographically pure organic solvent 3～8mL is injected the battery case that has taken out both positive and negative polarity and barrier film, slight vibration 3～5 times, leave standstill 20～30min, getting wherein, 1～2mL is transferred in the 2mL sample bottle; For without the lithium-ion battery electrolytes that uses, be to get electrolytic solution 2～10 μ L with the injection sampler to inject the 2mL sample bottle that 1～2mL chromatographically pure organic solvent has been housed in the preparation of step 1 testing sample, vibrate 3～5 times, leave standstill 10～20min.
3, the quantitative analysis method of a kind of lithium-ion battery electrolytes organic component according to claim 1 is characterized in that described analytical balance weighing method comprises:
The mass ratio of each organic component in A, the estimation testing sample, and with the reference standard of this mass ratio as the mass ratio of each organic component in the standard model of preparation;
B, be the mass value of 30～50 each organic component of gram basis of calculation sample according to the gross mass M of standard model of preparation;
C, get one of the clean small beaker of 100ml, utilize the accurate weighing mass value of analytical balance to be m
0
D, in beaker, add each organic component successively, and write down the gross mass value m that adds the back beaker respectively according to each organic component volatile grade order from small to large
i(i=1,2 ..., n, n are organic component number in the sample), in the interpolation process, should guarantee each mass value m that adds
i-m
I-1(i=1,2 ..., n, n are organic component number in the sample) meet the mass value of each organic component that calculates among the step B respectively as far as possible.
E, envelope beaker mouth utilize the magneton stirrer to stir 30～40min, leave standstill 10～20min, get this mixed liquor 2～10 μ L with the injection sampler then and inject the 2mL sample bottle that 1～2mL chromatographically pure acetone reagent has been housed, vibrate 3～5 times, leave standstill 10～20min, to be measured, be standard model; The mass ratio of each organic component of standard model is the quality ratio of known mi-mi-1, for simple and Convenient Calculation can represent to be that normalization is represented with percentages with it:
p
Ib=(m
i-m
I-1)/(m
i-m
0) * 100% (i=1,2 ..., n, n are organic component number in the sample).
4, the quantitative analysis method of a kind of lithium-ion battery electrolytes organic component according to claim 1 is characterized in that screening and definite object ion and characteristic ion may further comprise the steps:
A, utilize gas chromatograph-mass spectrometer (GCMS) that known each organic component quality is carried out the qualitative spectral scan analysis than the standard model of exact value, setting solvent time delay is 2.10～2.90min in this analytical approach, sample size 0.2～2.0 μ L, the injection port split ratio is 5: 1～20: 1, researchs and analyses the retention time of each the organic component chromatographic peak among the result and the retention time scope that factors such as width and shape are also determined the analytical test of each organic component thus thereof;
B, according to the screening scope of who high principle select target ion, in the pairing mass spectrogram of peak value retention time of the chromatographic peak of component to be measured, obtain the mass-to-charge ratio m/z value of the ion to be selected of 5 object ions; Select the screening scope of characteristic ion according to the singularity principle, select the ion that has feature mass-to-charge ratio m/z value most, in the pairing mass spectrogram of peak value retention time of the chromatographic peak of component to be measured, obtain the mass-to-charge ratio m/z value of the ion to be selected of 5 characteristic ions;
The selection analytical approach of C, target setting ion and characteristic ion is utilized all ions to be selected in the screening scope of selected ion monitoring mode monitoring standard sample, obtains a standard model ion flow collection of illustrative plates to be selected;
In D, the standard model ion flow collection of illustrative plates to be selected, the mass spectra peak intensity of each ion to be selected of each component is carried out integration to be added and calculates, add should be in full accord with the method for areal intensity for the integration that ion to be selected adopted of every group of close alternative in calculating, calculates the integrated intensity of all ions to be selected;
E, in every group of 5 ions to be selected, selected integrated intensity soprano is an employed ion in the final quantitative test; If the two integrated intensity value of integrated intensity soprano and integrated intensity differed less than 5% o'clock, should consider the influence of the integrated intensity of the ion to be selected before and after this two, should select position in the two at last and be employed ion in the final quantitative test near of integrated intensity third; If the integrated intensity value of integrated intensity third and integrated intensity fourth differed also less than 5% o'clock, still select the integrated intensity soprano to be employed ion in the final quantitative test.
5, the quantitative analysis method of a kind of lithium-ion battery electrolytes organic component according to claim 1, it is characterized in that selecting that the capillary column chromatography condition determination is in the ion method: chromatographic column is a quartz capillary column, column length 25～40m, internal diameter 0.25～0.50mm, thick 0.25～0.50 μ m of internal coating, the internal coating material is 5%-diphenyl-95%-dimethylsiloxane copolymer; Column temperature is heating schedule control, 30～60 ℃ of initial temperatures, and constant temperature time 1.00～2.50min is warming up to 140～180 ℃ with 5～15 ℃/min speed, constant temperature 8～15min; 240～300 ℃ of injector temperatures; Carrier gas is high-purity He, and pressure is 68.0～90.0KPa, total flow 9.0～15.0mL/min, and split ratio is 5: 1～20: 1.
6, the quantitative analysis method of a kind of lithium-ion battery electrolytes organic component according to claim 1 and 2 is characterized in that: organic solvent is acetone, isopropyl alcohol, ethanol, methylene chloride.
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| CN100368801C (en) * | 2006-07-21 | 2008-02-13 | 天津力神电池股份有限公司 | Method for measuring organic component in lithium ion cell electrolyte |
| CN104090060B (en) * | 2014-07-28 | 2015-10-28 | 广州天赐高新材料股份有限公司 | The detection method of residual solvent in electrolyte lithium salt |
| CN105449297B (en) * | 2015-12-28 | 2017-11-03 | 东莞新能源科技有限公司 | The quantitative analysis method of electrolyte consumption |
| CN105467058B (en) * | 2016-01-25 | 2017-05-17 | 惠州市豪鹏科技有限公司 | Method for detecting carboxylic ester compounds in lithium ion battery electrolyte |
| CN106124675B (en) * | 2016-06-13 | 2019-07-19 | 合肥国轩高科动力能源有限公司 | Method for pretreatment of lithium battery electrolyte chromatographic test |
| CN109725032B (en) * | 2017-10-27 | 2022-09-02 | 成都安普利菲能源技术有限公司 | High-flux electrolyte screening system and method thereof |
| CN109254105A (en) * | 2018-09-28 | 2019-01-22 | 桑顿新能源科技有限公司 | A method of utilizing lithium hexafluoro phosphate and other organic principles in gas chromatograph-mass spectrometer detection lithium-ion electrolyte |
| CN109541061A (en) * | 2018-11-30 | 2019-03-29 | 大同新成新材料股份有限公司 | A kind of lithium-ion battery electrolytes measured portions analysis method |
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Effective date of registration: 20161122 Address after: 255000 Shandong city of Zibo province high tech Zone Wei Guzhen Nanling Village Patentee after: SHANDONG KINGOLD AUTO ENGINEERING TECHNOLOGY CO.,LTD. Address before: Kwai Chung town Yanan Road, BYD Industrial Park in Longgang District of Shenzhen City, Guangdong province 518119 Patentee before: BYD Co.,Ltd. |
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Effective date of registration: 20170310 Address after: 255000 Zibo high tech Zone, Shandong Road, No. 135, high education park E block, Room 518 Patentee after: SHANDONG SINOGOLD AUTOMOBILE MANUFACTURING Co.,Ltd. Address before: 255000 Shandong city of Zibo province high tech Zone Wei Guzhen Nanling Village Patentee before: SHANDONG KINGOLD AUTO ENGINEERING TECHNOLOGY CO.,LTD. |
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Effective date of registration: 20210604 Address after: 255000 Shandong Zibo high tech Zone Guzhen Nanling New Village Patentee after: GUOJIN AUTOMOBILE GROUP Co.,Ltd. Address before: 255000 Room 518, block E, Gao Chuang garden, 135 Zheng Hui Road, hi tech Zone, Zibo, Shandong. Patentee before: SHANDONG SINOGOLD AUTOMOBILE MANUFACTURING Co.,Ltd. |
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Granted publication date: 20071114 |