CN112748103B - Method for measuring content of liquid electrolyte in battery - Google Patents
Method for measuring content of liquid electrolyte in battery Download PDFInfo
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- CN112748103B CN112748103B CN202011537341.4A CN202011537341A CN112748103B CN 112748103 B CN112748103 B CN 112748103B CN 202011537341 A CN202011537341 A CN 202011537341A CN 112748103 B CN112748103 B CN 112748103B
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- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000011244 liquid electrolyte Substances 0.000 title claims abstract description 20
- 239000012086 standard solution Substances 0.000 claims abstract description 85
- 239000003792 electrolyte Substances 0.000 claims abstract description 68
- 239000011259 mixed solution Substances 0.000 claims abstract description 54
- 150000002500 ions Chemical class 0.000 claims abstract description 52
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims description 23
- 229910001414 potassium ion Inorganic materials 0.000 claims description 13
- 229910001415 sodium ion Inorganic materials 0.000 claims description 13
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 10
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 8
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 8
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 6
- -1 cesium ions Chemical class 0.000 claims description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 6
- 150000003949 imides Chemical class 0.000 claims description 6
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical compound [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 claims description 5
- 150000007942 carboxylates Chemical class 0.000 claims description 4
- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910001419 rubidium ion Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 230000001133 acceleration Effects 0.000 claims 1
- 229910052792 caesium Inorganic materials 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 description 13
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 9
- 238000005070 sampling Methods 0.000 description 7
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 6
- 230000029087 digestion Effects 0.000 description 5
- 239000012470 diluted sample Substances 0.000 description 5
- 230000000284 resting effect Effects 0.000 description 5
- 239000012488 sample solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XXYVTWLMBUGXOK-UHFFFAOYSA-N [Na].FS(=N)F Chemical compound [Na].FS(=N)F XXYVTWLMBUGXOK-UHFFFAOYSA-N 0.000 description 2
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 2
- 229940006461 iodide ion Drugs 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- 229910021201 NaFSI Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
- G01N21/73—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited using plasma burners or torches
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Plasma & Fusion (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Engineering & Computer Science (AREA)
- Secondary Cells (AREA)
- Filling, Topping-Up Batteries (AREA)
Abstract
A method for determining the content of a liquid electrolyte in a battery is presented, comprising: preparing a standard solution with predetermined ions, wherein the predetermined ions are not contained in the electrolyte; preparing a battery of which the electrolyte content needs to be measured; adding a predetermined amount of standard solution into the battery, and mixing the standard solution with electrolyte in the battery to form a mixed solution; determining the concentration of predetermined ions in the mixed solution and the standard solution of unit mass; and determining the electrolyte mass in the battery. The determination method provided by the invention is simple to operate and easy to implement, and the detected content of the battery electrolyte is high in accuracy and small in error, and can be used for distinguishing solid-liquid batteries from liquid batteries, for example, and the feasibility is high.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a method for measuring the content of liquid electrolyte in a battery.
Background
With the development of electric vehicles and the development of power grid energy storage and small-sized energy storage demands in recent years, it is necessary to develop batteries which can be used in a wide temperature range and have high safety, high energy density and high power density. According to different application scenes, the electrolyte filling amount in the single battery can be several grams or tens to hundreds of grams, and as the electrolyte has potential safety hazards of easy leakage, easy volatilization, easy combustion and the like, how to conveniently and accurately detect the electrolyte content in the battery is an important link for ensuring the safety of battery products.
However, there is no specific method for detecting the electrolyte content in the battery, and thus, a practical method for conveniently measuring the electrolyte content in the battery is needed.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for measuring the content of liquid (such as liquid electrolyte) in a battery, which can realize the content test of the liquid (such as liquid electrolyte) in various batteries and is simple and easy to implement.
According to an exemplary embodiment, a method for measuring a content of a liquid electrolyte in a battery includes the steps of:
s1, preparing a standard solution with preset ions, wherein the electrolyte does not contain the preset ions;
s2: preparing a battery of which the content of liquid electrolyte needs to be measured;
s3: adding a predetermined amount of standard solution into the battery, and mixing the standard solution with electrolyte in the battery to form a mixed solution;
s4: determining the concentration of predetermined ions in the mixed solution and the standard solution of unit mass;
s5: determining the electrolyte mass in the cell, which is determined by the following formula:
wherein m is 1 M is the mass of the electrolyte 2 C, for the mass of the predetermined amount of standard solution 1 C is the predetermined ion concentration in the mixed liquid of unit mass 2 Is the predetermined ion concentration in the standard solution per unit mass.
In some examples, the predetermined ion contained in the standard solution may be sodium ion, potassium ion, rubidium ion, cesium ion, bromide ion, chloride ion, or iodide ion.
In some examples, the concentration of the predetermined ion in the standard solution is equal to or greater than 0.001mol/L, with the upper limit being its solubility in the standard solution, and the concentration is preferably 0.05 to 1mol/L.
In some examples, the standard solution may be prepared by dissolving one of sodium bis (trifluorosulfonyl) imide, sodium bis (fluorosulfonyl) imide, sodium acetate, potassium hexafluorophosphate, potassium bis (trifluorosulfonyl) imide, and potassium bis (fluorosulfonyl) imide in an organic solvent.
In some examples, the organic solvent is any one or a mixture of two or more of carbonate and/or carboxylate organic solvents, such as Ethylene Carbonate (EC), propylene Carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC) and carboxylate organic solvents (MF, MA, EA, MA, MP).
In some examples, in step S3, in order to ensure that the electrolyte and the standard solution are sufficiently mixed, after the mixed solution is left for a period of time, the mixed solution may be accelerated and mixed by using a mixing device such as a vibrator or a rotator.
In some examples, in step S4, a unit mass of the mixed solution and the standard solution may be taken from the mixed solution and the standard solution, the unit mass of the mixed solution and the standard solution may be fixed to the same volume, the concentration of the predetermined ion in the fixed volume of the mixed solution and the standard solution may be determined, and the concentration of the predetermined ion in the unit mass of the mixed solution and the standard solution may be determined according to the determined concentration of the predetermined ion in the fixed volume of the mixed solution and the standard solution.
In some examples, the battery is a lithium ion battery or a sodium ion battery.
In some examples, the battery is any one of a pouch battery, a prismatic battery, and a cylindrical battery.
The beneficial effects of the invention are as follows:
the method for measuring the electrolyte content is simple to operate and easy to implement, and the result of the electrolyte content measured by the method has high accuracy and small error (the error is less than 5%) compared with the actual content.
Other features and advantages of the present invention will become apparent from the description of exemplary embodiments.
Drawings
Fig. 1 shows a flowchart of a method of determining an electrolyte content in a battery according to an exemplary embodiment of the present invention.
Detailed Description
The invention is further illustrated by the following specific examples, which are provided for further illustration only and are not to be construed as limiting the scope of the invention.
Fig. 1 shows a flowchart of a method for measuring the content of a liquid electrolyte in a battery according to an exemplary embodiment of the present invention. As shown in fig. 1, the method 100 may begin at step S1 with preparing a standard solution having a predetermined ion, which may be selected based on the composition of the battery liquid electrolyte such that the predetermined ion is not present in the liquid battery electrolyte, and preferably the predetermined ion is not reactive with the electrolyte. In one example, the predetermined ion may be an alkali metal ion. For example, for a lithium ion battery, the predetermined ion may be selected from sodium ion, potassium ion, and for a sodium ion battery, the predetermined ion may be selected from potassium ion, rubidium ion, cesium ion. In one example, the predetermined ion may also be an anion, such as a halide ion, e.g., a bromide, chloride, or iodide ion.
In order to prepare the standard solution, in one embodiment, a salt compound of a predetermined ion and a solvent may be mixed and stirred. The compound used for the standard solution may be selected from one or more of sodium bis (trifluorosulfonyl) imide, sodium bis (fluorosulfonyl) imide, sodium acetate, potassium hexafluorophosphate, potassium bis (trifluorosulfonyl) imide and potassium bis (fluorosulfonyl) imide, and the solvent used for the standard solution may be selected from an organic solvent, for example, the same organic solvent as that in the lithium ion battery electrolyte, so that the subsequent uniform mixing of the standard solution and the electrolyte can be promoted, specifically, the organic solvent is any one or a mixture of two or more of Ethylene Carbonate (EC), propylene Carbonate (PC), dimethyl carbonate (DMC), ethyl Methyl Carbonate (EMC), diethyl carbonate (DEC) and a carboxylate organic solvent (MF, MA, EA, MA, MP). In some examples, the standard solution may be prepared by dissolving the compound in an organic solvent and mixing uniformly.
In some examples, the concentration of the predetermined ion in the standard solution is equal to or greater than 0.001mol/L, with an upper limit being its solubility in the standard solution. Since the method of determining the electrolyte content of the present invention does not require knowledge of the concentration of the predetermined ion in the standard solution, the present invention is not particularly limited, but in order to ensure the accuracy of the subsequent measurement of the predetermined ion, a standard solution having a concentration of 0.05 to 1mol/L, more preferably 0.1 to 0.5mol/L, may be preferably selected.
In step S2, a battery whose electrolyte content needs to be measured is prepared. The sequence of the step and the step S1 may be performed simultaneously or sequentially, which is not particularly limited in the present invention.
As described above, in some examples, the battery may be a lithium ion battery or a sodium ion battery. Specifically, the battery may be in the form of any one of a pouch battery, a prismatic battery, and a cylindrical battery.
Next, in step S3, a predetermined amount (m 2 ) And mixing the standard solution with the electrolyte in the battery to form a mixed solution. In one embodiment, the mass of the added standard solution may be determined based on the specifications of the liquid cell to ensure that the subsequent concentration determination for the predetermined ion is accurate. For example, for a filling quantity of several tens of gramsIt is conceivable to add 5-50g of standard solution.
In some examples, in step S3, in order to ensure that the electrolyte and the standard solution are sufficiently mixed, after the mixed solution is left to stand for a period of time, the mixed solution may be accelerated and mixed by using a vibration device such as a vibrator or a rotator, and the above standing and vibration steps may be repeated to make the concentration of the predetermined ions in the mixed solution uniform.
Next, in step S4, the concentration of predetermined ions in the mixed solution and the standard solution per unit mass is determined.
In one example, a unit mass of the mixed liquor, standard solution may be directly sampled and tested to determine the concentration of predetermined ions therein. The "unit mass" herein may be 1g, or may be other mass as long as the same mass of the sample extracted from the mixed solution and the standard solution is ensured.
To improve the test accuracy, in one example, a unit mass of the mixed solution and the standard solution can be taken from the mixed solution and the standard solution, respectively, the unit mass of the mixed solution and the standard solution are fixed to the same volume, and the concentration of the predetermined ion in the fixed volume of the mixed solution and the standard solution is measured, for example, denoted as c 1 ' and c 2 ' and determining the concentration of the predetermined ion in the mixed solution and the standard solution per unit mass based on the determined concentration of the predetermined ion in the mixed solution and the standard solution after the volume fixation, for example, by the determination of c 1 ' and c 2 ' multiplying the constant volume.
In one example, nitric acid may be added to the sample solution to digest the organic solvent, and then a solvent such as water may be added to dilute the sample solution to a predetermined volume, for example, 100-2000mL. The volume of the mixed solution and the standard solution after the sampling is subjected to volume fixing is not particularly limited, and the volume of the mixed solution and the standard solution after the sampling is subjected to volume fixing can be ensured only by diluting the mixed solution and the standard solution with unit mass to the same volume and ensuring the ion concentration measuring precision.
In one example, the concentration of the predetermined ions in the standard solution and the mixed solution after the volume is fixed can be measured by using an ICP-OES spectrometer, an ion chromatograph and other devices, and the ion concentration (the unit of the ion concentration can be μg/mL or mg/l) in the sample solution is recorded, and the content of the predetermined ions in the mixed solution and the standard solution in unit mass can be determined according to the measured concentration without performing density test, so that the test error of the content of the electrolyte introduced by the density test error is reduced.
Finally, in step S5, the electrolyte mass in the battery is determined, which can be determined by the following formula:
wherein m is 1 M is the mass of the electrolyte 2 C, for the mass of the predetermined amount of standard solution 1 C is the predetermined ion concentration in the mixed liquid of unit mass 2 Is the predetermined ion concentration in the standard solution per unit mass. As described above, in one example, m 1 、m 2 Can be in g, c 1 、c 2 May be in μg/mL.
In one example, c in the above equation is known by simple scaling 2 /c 1 C with the mixed solution and standard solution after the constant volume measured in the step S4 2 ’/c 1 ' equal, so in step S5, c can be used 2 ’/c 1 ' replace c in the above formula 2 /c 1 Thereby improving the convenience of operation.
It can be seen that the method for determining the electrolyte content of the battery is convenient, the electrolyte content in the liquid battery can be calculated by directly using the test values of the standard solution and the mixed solution and adding the mass of the standard solution into the battery, and the density test is not needed, so that the test error of the electrolyte content introduced by the density test error is reduced, the data conversion is not needed, and the test value (unit mug/mL) is not needed to be converted into the concentration value (unit mol/L) for calculation. Meanwhile, compared with the prior art, the method for measuring the electrolyte content has a plurality of advantages, for example, the test steps are simplified, a parallel sample is not required to be tested, and the electrolyte content in a single battery can be accurately tested.
The present invention will be described in further detail with reference to specific embodiments in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
(1) A pouch cell a was prepared, and the mass of the electrolyte in the pouch cell was previously determined to be 4g in order to verify the feasibility of the present invention.
(2) The method of the invention is used for measuring the quality of the electrolyte of the A soft package battery, and comprises the following specific steps:
s1: standard solutions were prepared with a sodium ion concentration of 0.05 mol/L: dissolving sodium difluorosulfimide (NaFSI) in an organic solvent, wherein the organic solvent is a mixture of Ethylene Carbonate (EC) and dimethyl carbonate (DMC) according to a mass ratio of 1:1, and adding 5.0g (m) of sodium difluorosulfimide into an A soft package battery 2 ) Mixing the standard solution with electrolyte in the soft-package battery to form mixed solution, and accelerating the mixing by using a vibrator;
s2: sampling after vibrating for 2 hours, resting for 12 hours and vibrating for 2 hours, and taking out the mixed solution to be tested;
s3: 1g of standard solution and 1g of mixed solution were taken. After digestion and volume setting are carried out to 100mL, detecting the concentration of sodium ions in the diluted sample solution by ICP-OES; recording and detecting the sodium ion concentration of the solution after volume fixing to 9.58 mug/mL (C Label (C) ) And 5.26. Mu.g/mL (C Mixing ) The method comprises the steps of carrying out a first treatment on the surface of the As in the previous analysis, the electrolyte content (m) in the pouch battery can be calculated and determined using the following formula and conversion 1 )：
According to the above formula, the mass m of the electrolyte 1 ＝4.11g；
The error between the electrolyte mass and the original mass of the soft package battery A obtained by the method is calculated as follows: (4.11-4)/4 x 100% = 2.8%.
Example 2
(1) A pouch battery B was prepared, in which the mass of the electrolyte was 9.6g.
(2) The method for measuring the quality of the electrolyte of the B soft package battery comprises the following specific steps:
s1: preparing a standard solution with the sodium ion concentration of 0.2 mol/L: dissolving NaTFSI in organic solvent, wherein the organic solvent is DMC solution, adding 10.0g (m) 2 ) Mixing the standard solution with electrolyte in the soft-package battery to form mixed solution, and accelerating the mixing by using a vibrator;
s2: sampling after vibrating for 3 hours, resting for 12 hours and vibrating for 3 hours, and taking out the mixed solution to be tested;
s3: 1g of standard solution and 1g of mixed solution were taken. After digestion and volume setting are carried out until the volume reaches 250mL, detecting the concentration of sodium ions in the diluted sample liquid by ICP-OES; the sodium ion concentration of the solution after constant volume was recorded to be 15.33. Mu.g/mL (C Label (C) ) And 7.89. Mu.g/mL (C Mixing ) The method comprises the steps of carrying out a first treatment on the surface of the The electrolyte content in the pouch cell was calculated using the following formula:
according to the above formula, the mass m of the electrolyte 1 ＝9.43g；
Calculating the error between the electrolyte mass and the original mass of the soft package battery B obtained by the method: (9.43-9.6)/9.6 x 100% = -1.8%.
Example 3
(1) A cylindrical battery C was prepared, in which the electrolyte mass was 7.8g.
(2) The method of the invention is used for measuring the mass of the electrolyte of the C cylindrical battery, and comprises the following specific steps:
s1: preparing a standard solution with potassium ion concentration of 0.25 mol/L: dissolving potassium hexafluorophosphate in an organic solvent, wherein the organic solvent is PC solution, adding 10.0g of standard solution into a C cylindrical battery, mixing the standard solution with electrolyte in the cylindrical battery to form a mixed solution, and accelerating the mixing by using a vibrator;
s2: sampling after vibrating for 3 hours, resting for 12 hours and vibrating for 3 hours, and taking out the mixed solution to be tested;
s3: 1g of standard solution and 1g of mixed solution were taken. After digestion and volume setting are carried out to 500mL, the concentration of potassium ions in the diluted sample solution is detected by ICP-OES; the potassium ion concentration of the measured solution was recorded to be 16.16. Mu.g/mL (C Label (C) ) And 8.96. Mu.g/mL (C Mixing ) The method comprises the steps of carrying out a first treatment on the surface of the The electrolyte content in the cylindrical battery was calculated using the following formula:
according to the above formula, the mass m of the electrolyte 1 ＝8.04g；
Calculating the error between the electrolyte mass and the original mass of the cylindrical battery C obtained by the method: (8.04-7.8)/7.8 x 100% = 3.01%.
Example 4
(1) A prismatic cell D, in which the mass of the electrolyte was 12.0g, was prepared.
(2) The method of the invention is used for measuring the mass of the electrolyte of the D square battery, and comprises the following specific steps:
s1: preparing a standard solution with potassium ion concentration of 0.5 mol/L: dissolving potassium hexafluorophosphate in an organic solvent, wherein the organic solvent is PC solution, adding 13.0g of standard solution into the D square battery, mixing the standard solution with electrolyte in the square battery to form a mixed solution, and accelerating the mixing by using a vibrator;
s2: sampling after vibration for 4 hours, resting for 12 hours and vibration for 4 hours, and taking out the mixed solution to be tested;
s3: 1g of standard solution and 1g of mixed solution were taken. After digestion and volume setting are carried out to 1000mL, the concentration of potassium ions in the diluted sample solution is detected by ICP-OES; the potassium ion concentration of the measured solution was recorded to be 16.10. Mu.g/mL (C Label (C) ) And 8.45. Mu.g/mL (C Mixing ) The method comprises the steps of carrying out a first treatment on the surface of the The following formula is adoptedCalculating the electrolyte content in the square battery:
according to the above formula, the mass m of the electrolyte 1 ＝11.77g；
Calculating the error between the electrolyte mass and the original mass of the square battery D obtained by the method: (11.77-12.0)/12.0 x 100% = -1.92%.
Example 5
(1) A prismatic battery E, in which the mass of the electrolyte was 20.0g, was prepared.
(2) The method of the invention is used for measuring the mass of the electrolyte of the E square battery, and comprises the following specific steps:
s1: preparing a standard solution with the potassium ion concentration of 1 mol/L: dissolving potassium bis (fluorosulfonyl) imide (KFSI) in an organic solvent, wherein the organic solvent is methyl ethyl carbonate (EMC), adding 30.0g of standard solution into an E square battery, mixing the standard solution with electrolyte in the square battery to form a mixed solution, and accelerating the mixing by using a vibrator;
s2: sampling after shaking for 4 hours, resting for 24 hours and shaking for 6 hours, and taking out the mixed solution to be tested;
s3: 1g of standard solution and 1g of mixed solution were taken. After digestion and volume setting of 2000mL, detecting the concentration of potassium ions in the diluted sample solution by ICP-OES; the potassium ion concentration of the measured solution was recorded to be 16.14. Mu.g/mL (C Label (C) ) And 9.78. Mu.g/mL (C Mixing ) The method comprises the steps of carrying out a first treatment on the surface of the The electrolyte content in the prismatic cell was calculated using the following formula:
according to the above formula, the mass m of the electrolyte 1 ＝19.51g；
Calculating the error between the electrolyte mass and the original mass of the square battery E obtained by the method: (19.51-20.0)/20.0 x 100% = -2.45%.
According to the specific implementation and test results of the embodiment 1, the embodiment 2, the embodiment 3, the embodiment 4 and the embodiment 5, the method provided by the invention is simple, the test result has high accuracy and small error (lower than 5%), can be used for accurately detecting the electrolyte content in the battery, has strong operability, and can be applied to various occasions, for example, is convenient and feasible for distinguishing the liquid battery from the solid-liquid battery.
The above is a further detailed description of the invention in connection with specific preferred embodiments, and it is not to be construed as limiting the practice of the invention to these descriptions. It will be apparent to those skilled in the art that several simple deductions or substitutions may be made without departing from the spirit of the invention, and these shall be considered to be within the scope of the invention.
Claims (8)
1. A method for determining the level of liquid electrolyte in a battery comprising the steps of:
s1, preparing a standard solution with preset ions, wherein the preset ions are not contained in the electrolyte, and the preset ions contained in the standard solution are sodium ions, potassium ions, rubidium ions, cesium ions, bromide ions, chloride ions or iodide ions;
s2: preparing a battery of which the content of liquid electrolyte needs to be measured;
s3: adding a predetermined amount of standard solution into the battery, and mixing the standard solution with liquid electrolyte in the battery to form a mixed solution;
s4: determining the concentration of predetermined ions in the mixed solution and the standard solution of unit mass;
s5: determining the electrolyte mass in the cell, which is determined by the following formula:
wherein m is 1 M is the mass of the electrolyte 2 For the predetermined amount of standard solutionMass, c 1 C is the predetermined ion concentration in the mixed liquid of unit mass 2 Is the predetermined ion concentration in the standard solution per unit mass,
wherein the standard solution is prepared by dissolving the salt compound of the preset ion in an organic solvent, mixing and stirring,
in step S4, a unit mass of mixed solution and standard solution are taken from the mixed solution and standard solution, the volume of the unit mass of mixed solution and standard solution is fixed to the same volume, the concentration of predetermined ions in the mixed solution and standard solution after the volume fixing is measured, and the concentration of predetermined ions in the unit mass of mixed solution and standard solution is determined according to the measured concentration of predetermined ions in the mixed solution and standard solution after the volume fixing.
2. The method for determining the content of a liquid electrolyte in a battery according to claim 1, wherein the concentration of the predetermined ion is equal to or greater than 0.001mol/L.
3. The method for determining the content of a liquid electrolyte in a battery according to claim 2, wherein the concentration of the predetermined ion is 0.05 to 1mol/L.
4. The method for measuring the content of the liquid electrolyte in the battery according to claim 1, wherein the salt compound of the predetermined ion is one of sodium bis (trifluorosulfonyl) imide, sodium bis (fluorosulfonyl) imide, sodium acetate, potassium hexafluorophosphate, potassium bis (trifluorosulfonyl) imide and potassium bis (fluorosulfonyl) imide.
5. The method for measuring the content of the liquid electrolyte in the battery according to claim 4, wherein the organic solvent is any one or a mixture of two or more of Ethylene Carbonate (EC), propylene Carbonate (PC), dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), diethyl carbonate (DEC) and a carboxylate organic solvent.
6. The method for measuring the content of the liquid electrolyte in the battery according to claim 1, wherein in the step S3, after the mixed liquid is left for a certain period of time, the mixed liquid is mixed with acceleration by using a vibrator or a rotator.
7. The method of determining the level of liquid electrolyte in a battery of claim 1, wherein the battery is a lithium ion battery or a sodium ion battery.
8. The method for measuring the liquid electrolyte content in a battery according to claim 7, wherein the battery is any one of a pouch battery, a prismatic battery and a cylindrical battery.
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