CN109708990A - The measuring method of trace moisture content in a kind of electrode material for lithium ion cell - Google Patents
The measuring method of trace moisture content in a kind of electrode material for lithium ion cell Download PDFInfo
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- CN109708990A CN109708990A CN201811409315.6A CN201811409315A CN109708990A CN 109708990 A CN109708990 A CN 109708990A CN 201811409315 A CN201811409315 A CN 201811409315A CN 109708990 A CN109708990 A CN 109708990A
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- 239000007772 electrode material Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 37
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 84
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims description 38
- 238000007789 sealing Methods 0.000 claims description 27
- 238000009835 boiling Methods 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 238000001514 detection method Methods 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 230000004580 weight loss Effects 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 229920002379 silicone rubber Polymers 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 2
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910021385 hard carbon Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229910021384 soft carbon Inorganic materials 0.000 claims description 2
- 238000004448 titration Methods 0.000 claims description 2
- 238000003556 assay Methods 0.000 claims 10
- 239000010405 anode material Substances 0.000 claims 3
- 238000007429 general method Methods 0.000 claims 2
- 239000004793 Polystyrene Substances 0.000 claims 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims 1
- 239000011261 inert gas Substances 0.000 claims 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims 1
- 238000002844 melting Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- 229920002223 polystyrene Polymers 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 239000004945 silicone rubber Substances 0.000 claims 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims 1
- 238000005259 measurement Methods 0.000 abstract description 12
- 239000007773 negative electrode material Substances 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 239000007774 positive electrode material Substances 0.000 abstract 1
- 239000012453 solvate Substances 0.000 description 9
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 229910017052 cobalt Inorganic materials 0.000 description 7
- 239000010941 cobalt Substances 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- 229910052493 LiFePO4 Inorganic materials 0.000 description 6
- 208000016261 weight loss Diseases 0.000 description 5
- 239000004305 biphenyl Substances 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 125000006267 biphenyl group Chemical group 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000013585 weight reducing agent Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- 238000003109 Karl Fischer titration Methods 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000881 depressing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 208000020442 loss of weight Diseases 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000011410 subtraction method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000010200 validation analysis Methods 0.000 description 1
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- Sampling And Sample Adjustment (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明公开了一种锂离子电池用电极材料中微量水分含量的测定方法，其包括：根据克拉珀龙方程以及气压‑水沸点的关系选择合适的样品容器，按照特定的样品容器容积与样品称样量的关系，将待测电极材料放入样品容器中；再以一个合理的温度对盛有样品的样品容器加热，使样品中的水分充分蒸发出并冷凝在样品容器壁上；然后采用经过卡尔费休预滴定过的、水分含量极低的甲醇溶剂溶解样品容器中的水分，以尽可能的降低测量背景干扰。最后，采用卡尔费休微量水分测试仪，通过排除样品容器内非饱和气体对水蒸气吸收的干扰以及背景值的干扰后，计算样品中的水分含量。本发明提供的测定方法，实现方式简单，易于操作；本方法的测定结果重复性好，准确度高；本方法适用于极大多数的正负极材料，应用广泛。The invention discloses a method for measuring trace moisture content in electrode materials for lithium ion batteries. The relationship between the sample size, put the electrode material to be tested into the sample container; then heat the sample container containing the sample at a reasonable temperature, so that the water in the sample can be fully evaporated and condensed on the wall of the sample container; The Karl Fischer pre-titrated methanol solvent with very low water content dissolves the water in the sample container to minimize measurement background interference. Finally, a Karl Fischer trace moisture tester was used to calculate the moisture content in the sample by eliminating the interference of the unsaturated gas in the sample container on the absorption of water vapor and the interference of the background value. The determination method provided by the invention is simple in implementation and easy to operate; the determination result of the method has good repeatability and high accuracy; the method is suitable for most positive and negative electrode materials and is widely used.
Description
Technical field
The present invention relates to trace moisture content determination techniques fields, more specifically, it relates to which a kind of lithium ion battery is used
The measuring method of trace moisture content in electrode material.
Background technique
Lithium ion battery is because of its own excellent properties, in portable electronic information equipment, new energy power vehicle, small
The fields such as type electric vehicle and power energy storage, which achieve, to be widely applied.At this stage, lithium ion battery just towards high security,
High-energy density, high power density, long circulation life direction are developed.The realization of this target, be unable to do without its own raw material
Optimization.The raw material for constituting lithium ion battery specifically include that positive electrode, negative electrode material, electrolyte and diaphragm, wherein positive material
Material together with negative electrode material and referred to as electrode material.Influenced by factors such as production technology, transport, storages, in electrode material or
It is more or few there is the moisture of certain content.After these moisture are dissolved into battery with electrode material, can in electrolyte
Lithium salts reacts to form hydrogen fluoride, and the pressure of inside battery is caused to increase, so as to cause battery blow-up, the danger such as leakage.This
Outside, the hydrogen fluoride that moisture reacts generation with electrolyte can also be with solid electrolyte interface film (the Solid electrolyte of cathode
Interphase, SEI) reaction, lithium fluoride precipitating is generated, while destroying SEI film, sends out lithium ion in battery cathode sheet
Raw irreversible chemical reaction, consumes active lithium-ion, thereby reduces the capacity of battery.For this reason, it may be necessary in electrode material
Strict control moisture in production process, and electrode material purchase and sale link in reinforce moisture content detection.
Remaining moisture is generally several hundred a ppm in electrode material, and in contrast content is lower, general using dry loss of weight
Method or Karl_Fischer method measurement, the standard for using for reference reference includes: that " determination of moisture is general in chemical products by GB/T 6284-2006
Method dries weight reduction " and GB/T 6283-2008 " measurement Karl_Fischer method (the general side of moisture content in chemical products
Method) ".Wherein, GB/T 6284-2006 " the dry weight reduction of the universal method of determination of moisture in chemical products " passes through 105 DEG C of temperature
Sample is heated, using the reduced value of balance measurement heating front and back example weight after its moisture sufficiently evaporates, in this, as moisture
Content value.But electrode material higher for volatile organic content, after 105 DEG C of temperature heat, volatile organic matter
Reduction will lead to the bigger than normal of moisture measurement result.For this purpose, industry is generally tended to select in measuring chemical products when micro-moisture
The high Karl_Fischer method of specificity is selected, using GB/T 6283-2008 " the measurement Karl_Fischer method of moisture content in chemical products
(universal method) ".It but is that sample dissolves in the organic solvent in karl Fischer titration cup using the premise of this method standard
(methanol, chloroform, glacial acetic acid etc.).And lithium ion battery electrode material can not be dissolved in organic solvent, it is therefore desirable to be directed to lithium
Ion battery electrode materials specially design a kind of karl Fischer measuring method of micro-moisture.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide in a kind of electrode material for lithium ion cell
The measuring method of trace moisture content, this method have easy to operate, and accuracy is higher, repeated preferable advantage, can meet
The detection demand of lithium ion battery industry.
To achieve the above object, the present invention provides the following technical scheme that it is micro- in a kind of electrode material for lithium ion cell
Measure the measuring method of moisture content, comprising the following steps:
(1) the open sample container after taking 3 identical abundant dryings and being fully cooled, is denoted as 0 respectively#、1#、2#Sample container,
At room temperature, it weighs powdered electrode material sample to be measured and is put into 1#In sample container and jolt ramming is smooth to sample surfaces, then claims
The electrode material sample to be measured of Double Weight is taken to be put into 2#In sample container and jolt ramming is smooth to sample surfaces, and 0#Sample container is made
For blank not setting-out product, and seal 0#、1#、2#The open-mouth of sample container；The pass of sample container volume and weighed sample quality
System determines as follows: the sample amount of weighing heats described 2 it is ensured that in subsequent step (2) with T1 temperature#Sample container
When, described 2#The heating temperature T3 of all samples is all larger than the boiling point T2 of water when air pressure is P1 in sample container in sample container,
Wherein P1 is 2 at a temperature of T1#The moisture of sample all becomes after steam in sample container and internal temperature is increased to dynamic
Pressure after balance in container；
(2) with 0 of sealing in temperature T1 heating stepses (1)#Sample container and fill sample, sealing 1#、2#Sample container
2h~4h, until 1#、2#The moisture in electrode material sample to be measured in sample container sufficiently evaporates；Subsequent natural cooling 30min
More than, the vapor for evaporating sample sufficiently condenses on the wall；
(3) karl Fischer trace moisture tester is opened, using anhydrous methanol as solvent, moisture is carried out by instrument specification and drips in advance
It is fixed, until drift value less than 10 μ L/min, obtains the methanol solvate that moisture titrated in advance；
(4) extractor after taking an abundant drying and being fully cooled, the methanol solvate and equivalent that aspiration step (3) obtains are added to
The 0 of cooling in step (2)#、1#、2#In sample container, then still sealed sample container, and each sample container is sufficiently shaken,
It is completely dissolved in the condensed water being attached on sample container wall in methanol solvate；Wherein, the volume aspirated and sample of methanol solvate
The relationship of the volume of product container is 1:4~1:2；
(5) to 0 in step (4)#Methanol solvate in sample container and 1#、2#Obtained methanol-sample in sample container
Mixed solution measures moisture value using karl Fischer trace moisture tester respectively, and correspondence is denoted as A, B, C；If B is greater than A, explanation
1#Vapor in sample container in gas is saturation state, and the moisture content of sample can be calculated by step (6).If B is equal to
A illustrates 1#Vapor in sample container in gas is lower than instrument detection limit for the moisture content of unsaturated state or sample,
It answers return step (1), is re-measured again after increasing sample size.
(6) (I) calculates biodiversity percentage composition W in electrode material sample to be measured according to the following formula:
In formula (I):
1 in B --- step (1)#The moisture value of electrode material sample to be measured, unit g in sample container；
2 in C --- step (1)#The moisture value of electrode material sample to be measured, unit g in sample container；
m1--- 1 in step (1)#The weight of electrode material sample to be measured, unit g in sample container；
m2--- 2 in step (1)#The weight of electrode material sample to be measured, unit g in sample container；
w1--- 1 measured in step (5)#The biodiversity percentage composition of electrode material sample to be measured, % in sample container；
w2--- 2 measured in step (5)#The biodiversity percentage composition of electrode material sample to be measured, % in sample container.
Preferably, the sample container is glass container, heating of the sample container sealed in step (1) in step (2)
The pressure of the standard atmospheric pressure of at least two or more, i.e., the pressure of the additional standard atmospheric pressure more than at least one can be born in the process
By force.
It is highly preferred that the sealing cover in step (1) using lid conjunction in sample container open-mouth realizes the close of sample container
Envelope；The sealing cover includes a metal cap body, and the central part of metal cap body is provided with through-hole, and metal cap body is corresponded to and set at lead to the hole site
There is gasket seal, gasket seal has size identical with the open size of sample container；The gasket seal by silicon rubber with
The composite material of polytetrafluoroethylene (PTFE) is made.
Preferably, in step (2), judge 1#、2#The moisture in electrode material sample to be measured in sample container is sufficiently steamed
Mode out are as follows: firstly, weigh appropriate amount of sample, according to the GB/T 6284-2006 " universal method of determination of moisture in chemical products
Dry weight reduction " it is dried, and assume that the part of weight loss is moisture, calculate the quality point of moisture in sample
Number；Then, the amount n for calculating the substance of sample contained humidity in sample container, together with heating source when heating sample in step (2)
Temperature T1 substitute into Clapeyron equation PV=nRT (in formula: P be confined space in air pressure；V is shared by gas in confined space
According to volume；N is the amount of the substance of gas in confined space；R is gas constant；T is the temperature of gas in confined space), meter
After the moisture that the amount for calculating substance in sample container is n all becomes steam, the pressure P1 in sample container；Further according to different gas
The boiling point table of comparisons for depressing water, obtains boiling point T2 of the water in pressure P1；If heating sample container with the temperature T1 of step (2)
When, the heating temperature T3 of sample is above the boiling point T2, then " determination of moisture is general in chemical products referring to GB/T 6284-2006
Method dry weight reduction " as defined in heating time, sample container through 2h~4h heating after, the moisture in sample can sufficiently be steamed
Hair；If heat sample container with the temperature T1 of step (2), the heating temperature T3 of sample is equal to or less than boiling point T2, then adjusts
High-temperature T1, the T2 until the heating temperature T3 of sample is above the boiling point.Moreover, it is judged that whether the heating temperature T3 of sample is above the boiling point
The mode of T2 are as follows: weighed sample is put into an open-top receptacle simultaneously jolt ramming, a kind of solid of the fusing point slightly larger than T2 is selected to refer to
Show that agent is placed on the top of sample in open-top receptacle and jolt ramming；After sealing open-top receptacle, place it on heating source in step (2)
The temperature of the T1 heats；If the solid indicator above sample melts, show that sample can be made by heating source temperature T1
The temperature T3 of product whole region is all larger than the boiling point T2 of water.It is influenced by heat transfer and heat radiation, container when heating sample container
Interior temperature can be much smaller than the temperature T1 of heating source, calculate Clapeyron equation by the temperature T1 of heating source, it can be ensured that sample weighting amount,
It is sufficiently matched between the volume and heating temperature three of sample container.
Preferably, karl Fischer trace moisture tester is stored in water before use, oxygen content is respectively less than the lazy of 0.1ppm
In property atmosphere glove box.
Preferably, in step (3), methanol is HPLC grades, and the mass fraction of contained humidity is less than 0.02%.
Preferably, in step (4), the extractor is injector for medical purpose.
It is highly preferred that during methanol solvate is added into three sample containers, being taken another abundant in step (4)
Injector for medical purpose after drying and being fully cooled, pulls up syringe needle, and the exposed gasket seal position of the syringe needle Self-sealed lid is inserted
Enter in sample container, sample container is kept to be communicated with the atmosphere.
Preferably, the D50 partial size of the electrode material sample to be measured is 0.5~30 micron；The electrode material to be measured is
Cobalt acid lithium, LiFePO4, nickle cobalt lithium manganate, nickel cobalt lithium aluminate, LiMn2O4, graphite, lithium titanate or silicon-carbon cathode material, soft carbon are negative
Pole material, hard carbon cathode material etc..
Measuring method provided by the invention, implementation is simple, easily operated；The measurement result of this method is reproducible,
Accuracy is high；This method is suitable for the positive and negative pole material of thumping majority, is widely used.
Specific embodiment
In following embodiment and test, sample container uses diameter for 15mm, volume 20mL, high about 11cm opening cylinder
Shape vial, open-mouth are sealed using sealing cover.Sealing cover includes an aluminum lid, and the cover center portion is corresponding logical
Hole location is equipped with gasket seal, and gasket seal is made of the composite of silicon rubber and polytetrafluoroethylene (PTFE), and has and sample
The shape and size that the opening of container matches.Extractor uses injector for medical purpose.
Embodiment 1
1) it takes 4 cylindrical glass bottles to be put into air dry oven as sample container, is done under the conditions of 103 DEG C~110 DEG C
Dry sample container 4h.
2) sealing cover 4 and 20mL injector for medical purpose 2 are taken, is put into vacuum oven, is less than to pressure in case together
After 1000Pa, 50 DEG C are warming up to, dries sealing cover and injector for medical purpose 4h.
3) sample container, sealing cover, injector for medical purpose after will be dry in step 1) and step 2) be put into cold in drier
But 20min.
4) 1 sample container and sealing cover at room temperature at 20 DEG C or so, are taken out from drier, are weighed using electronic balance
2g cobalt acid lithium sample (D50 partial size be 19 microns) is put into sample container and jolt ramming is smooth to sample surfaces, then toward above sample
Put two hydrazine of 0.2g diphenyl phosphinylidyne (about 170 DEG C of fusing point or so) and jolt ramming.Using being put it to after seal cap sealing sample container
On plate type electromagnetic furnace with 290 DEG C after several minutes of heating sample container, two hydrazine of diphenyl phosphinylidyne melts, and at this time in sample
The boiling point of water is less than the fusing point of two hydrazine of diphenyl phosphinylidyne, shows that the sample container for heating the specification with 290 DEG C can make in it
The whole region of portion 2g cobalt acid lithium sample below is greater than the boiling point of water.
5) remaining sample container, sealing cover at room temperature at 20 DEG C or so, are taken out from drier, are claimed using electronic balance
1g cobalt acid lithium sample (D50 partial size is 19 microns) is taken to be put into 1#In sample container and jolt ramming is smooth to sample surfaces, then weighs 2g
Same cobalt acid lithium sample is put into 2#In sample container and jolt ramming is smooth to sample surfaces, and the Container Tag of non-setting-out product is 0#, will
Sealing cover covers tightly on 3 sample containers.
6) 3 sample containers are put into vertically above plate type electromagnetic furnace, temperature is adjusted to 290 DEG C, continuous heating sample 2h.
Sample container is removed from electromagnetic oven again, makes its natural cooling 30min.
7) karl Fischer trace moisture tester is opened, (HPLC grades, the mass fraction of moisture is less than with anhydrous methanol
0.02%) it is solvent, carries out moisture by instrument specification and titrate in advance, until drift value is less than 10 μ L/min.
8) injector for medical purpose one after selecting step (2) is dry, syringe needle is pulled out, syringe needle Self-sealed lid through hole is exposed
Gasket seal position insertion 0#In sample container, then with another injector for medical purpose after step (2) are dry draw karr
Take the methanol solvate 16mL in not titration cup, to 0#5mL methanol is injected in sample container, then is pulled up syringe needle and be sequentially inserted into 1#With
2#In sample container, and to 1#With 2#5mL methanol is injected in sample container respectively, then pulls up syringe needle.Sufficiently shake each sample
Container is substantially soluble in the moisture on chamber wall in methanol.
9) 3 sample container bottle caps are successively quickly opened, by 0#Methanol solvate in sample container and 1#、2#Sample holds
Obtained methanol-sample mixed solution is respectively poured into karl Fischer trace moisture tester in device, measures moisture value.Experiment
Show 1#Moisture value B in sample container is greater than 0#Moisture value A in sample container, so calculating sample moisture by formula (I)
Content (mass fraction).
Repeat the above steps 1) -9) three times, unlike step (1) and step (2) respectively with 3 sample containers and 3
A sample lid, and step (4) are omitted, measurement result is shown in Table 1.Since sample number is less than 8, standard deviation is calculated using range method
Relative standard deviation is acquired divided by measurement average value again afterwards.Standard deviation S=R/C, R is very poor in formula, and C is very poor coefficient.Sample
Very poor coefficient when this number is 3 is 1.69.
Table 1
As it can be seen from table 1 measure 1#In sample container sample moisture content average value be 0.36mg, 2#Sample in sample container
Product moisture content average value is 0.56mg, relative standard deviation 0.0%.
10) moisture content (mass fraction) W in cobalt acid lithium sample is calculated according to formula (I) is 0.02%.
Embodiment 2
It is measured using the method for embodiment 1, unlike, 1.0g LiFePO4 sample (D50 granularity is weighed in step (4)
It is 0.5 micron) it is put into sample container.0.5g LiFePO4 sample (0.5 micron of D50 granularity) is weighed in step (5) is put into 1#
Sample container weighs 1.0g LiFePO4 sample and is put into 2#Sample container.
The measurement result of step (9) is shown in Table 2.
Table 2
From table 2 it can be seen that measure 1#Sample moisture average value is 1.73mg, sample water in 2# sample container in sample container
Dividing average value is 3.16mg, and relative standard deviation is less than 6.7%；
In step 10), moisture content (mass fraction) W being calculated in LiFePO4 sample according to formula (I) is
0.285%.
Embodiment 3
It is measured using the method for embodiment 1, unlike, 1.0g graphite sample is weighed in step (4), and (D50 granularity is 13
Micron) it is put into sample container.0.5g graphite sample (13 microns of D50 granularity) is weighed in step (5) is put into 1#Sample container claims
1.0g graphite sample is taken to be put into 2#Sample container.
The measurement result of step (9) is shown in Table 3.
Table 3
From table 3 it can be seen that measure 1#In sample container sample moisture average value be 0.11mg, 2#Sample water in sample container
Dividing average value is 0.2mg, and relative standard deviation is less than 12.5%；
In step 10), it is 0.019% that moisture content (mass fraction) W in graphite sample, which is calculated, according to formula (I).
Accuracy validation test
For the accuracy for showing this method measurement result, this method is verified using recovery of standard addition.
1) 2 cylindrical glass bottles are taken to be put into air dry oven as sample container, in 103 DEG C~110 DEG C conditions
Lower drying sample container 4h.
2) sealing cover 2 and 20mL injector for medical purpose 2 are taken, is put into vacuum oven, is less than to pressure in case together
After 1000Pa, 50 DEG C are warming up to, dries sealing cover and injector for medical purpose 4h.
3) sample container, sealing cover, injector for medical purpose after will be dry in step 1) and step 2) be put into cold in drier
But 20min.
4) 1.0g cobalt acid lithium sample is weighed, is put into the sample container of step (3) and with seal cap sealing, is labeled as 1#。
The sample for weighing same weight again is put into the sample container of step (3), using the microsyringe (range of Agilent company
10 μ L, 0.2 μ L of precision) 10.0 μ L or so pure water is pipetted, the rear seal cap sealing of 5.0 μ L or so in sample is instilled, is labeled as 2#。
Using the balance of a ten thousandth precision, instillation 2 is accurately calculated by Subtraction method#The quality of pure water in sample container.
5) it is computed, volume becomes 6.2mL or so after 5.0 μ L pure water become vapor, and gas pressure intensity becomes in sample container
(since the moisture content in each sample is respectively less than 0.3mg, become so ignoring moisture in sample for 1.31 standard atmospheric pressures or so
For the influence after steam to air pressure in sample container).Assuming that temperature when internal gas balances is electricity after sample bottle is heated
290 DEG C of the heating temperature of magnetic furnace, it is about 2.7 standard atmospheric pressures that air pressure in sample container under this condition, which is calculated, and sample holds
Less than 133 DEG C of the boiling point of water (boiling point of water when 3 standard atmospheric pressures) in device, and the heating temperature of each sample is all larger than at this time
170 DEG C (greater than the fusing point of two hydrazine of diphenyl phosphinylidyne).With 290 DEG C of heating sample container 2h~4h, the water in container in sample can
Sufficiently to be evaporated.
It is 6) the sample jolt ramming in 1# sample container, 2# sample container is latter with being vertically put into above plate type electromagnetic furnace,
Temperature is adjusted to 290 DEG C, continuous heating sample 2h.Sample container is removed from electromagnetic oven again, makes its natural cooling 30min.
7) karl Fischer trace moisture tester is opened, (HPLC grades, the mass fraction of moisture is less than with anhydrous methanol
0.02%) it is solvent, carries out moisture by instrument specification and titrate in advance, until drift value is less than 10 μ L/min.
8) injector for medical purpose one after selecting step (2) is dry, syringe needle is pulled out, by the exposed sealing of syringe needle Self-sealed lid
Pads placement insertion 1#In sample container, then karl Fischer is drawn with another injector for medical purpose after step (2) are dry and is dripped
The methanol solvate 12mL in cup is determined, first to 1#5mL methanol is injected in sample container, then is pulled up syringe needle and be inserted into 2#In sample container,
And to 2#5mL methanol is injected in sample container, then pulls up syringe needle.Each sample container is sufficiently shaken, the water on chamber wall is made
Divide and is substantially soluble in methanol.
9) 1 is successively quickly opened#、2#Sample container bottle cap, methanol-sample mixed solution in each sample container is each
From pouring into karl Fischer trace moisture tester, moisture value is measured.Sample moisture content is calculated by formula (I).
10) weigh 1.0g graphite and 0.1g LiFePO4 respectively again, repeat 1) -9) the step of, obtain table 4.
4 recovery of standard addition test result of table
As can be seen from Table 4, the recovery of standard addition of the method for the present invention is between 90%~100%, accuracy with higher.
This specific embodiment is only explanation of the invention, is not limitation of the present invention, those skilled in the art
Member can according to need the modification that not creative contribution is made to the present embodiment after reading this specification, but as long as at this
All by the protection of Patent Law in the scope of the claims of invention.
Claims (10)
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| CN110982278A (en) * | 2019-12-24 | 2020-04-10 | 深圳德邦界面材料有限公司 | Low-volatilization heat-conducting gasket and preparation method thereof |
| CN111579711A (en) * | 2020-04-24 | 2020-08-25 | 江苏中兴派能电池有限公司 | Method for evaluating water content of baked lithium ion battery |
| CN111624300A (en) * | 2020-07-01 | 2020-09-04 | 内蒙古通威高纯晶硅有限公司 | Moisture determination method and moisture determination device |
| CN112051319A (en) * | 2020-09-02 | 2020-12-08 | 东莞瑞泰新材料科技有限公司 | Oily carbon nanotube conductive slurry moisture testing device and testing method |
| CN112255301A (en) * | 2020-09-28 | 2021-01-22 | 陕西黄陵煤化工有限责任公司 | Method for measuring moisture of liquid anhydrous ammonia |
| CN113155935A (en) * | 2021-04-12 | 2021-07-23 | 山西钢科碳材料有限公司 | Method for measuring moisture content in azo initiator |
| CN115290814A (en) * | 2022-08-09 | 2022-11-04 | 多氟多新材料股份有限公司 | Determination method of moisture content in lithium difluorophosphate |
| CN115629151A (en) * | 2022-10-11 | 2023-01-20 | 长沙矿冶研究院有限责任公司 | Characterization method of trace moisture in conductive paste |
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| CN110982278A (en) * | 2019-12-24 | 2020-04-10 | 深圳德邦界面材料有限公司 | Low-volatilization heat-conducting gasket and preparation method thereof |
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| CN112255301A (en) * | 2020-09-28 | 2021-01-22 | 陕西黄陵煤化工有限责任公司 | Method for measuring moisture of liquid anhydrous ammonia |
| CN113155935A (en) * | 2021-04-12 | 2021-07-23 | 山西钢科碳材料有限公司 | Method for measuring moisture content in azo initiator |
| CN115290814A (en) * | 2022-08-09 | 2022-11-04 | 多氟多新材料股份有限公司 | Determination method of moisture content in lithium difluorophosphate |
| CN115629151A (en) * | 2022-10-11 | 2023-01-20 | 长沙矿冶研究院有限责任公司 | Characterization method of trace moisture in conductive paste |
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