CN113851666A - Electrolyte of primary lithium battery and preparation method and application thereof - Google Patents
Electrolyte of primary lithium battery and preparation method and application thereof Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 131
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 54
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 117
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 46
- 239000003960 organic solvent Substances 0.000 claims abstract description 36
- 238000002156 mixing Methods 0.000 claims abstract description 18
- VLJQDHDVZJXNQL-UHFFFAOYSA-N 4-methyl-n-(oxomethylidene)benzenesulfonamide Chemical compound CC1=CC=C(S(=O)(=O)N=C=O)C=C1 VLJQDHDVZJXNQL-UHFFFAOYSA-N 0.000 claims abstract description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011737 fluorine Substances 0.000 claims abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 5
- 239000012948 isocyanate Substances 0.000 claims abstract description 5
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 8
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000002516 radical scavenger Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 6
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 6
- CAQYAZNFWDDMIT-UHFFFAOYSA-N 1-ethoxy-2-methoxyethane Chemical compound CCOCCOC CAQYAZNFWDDMIT-UHFFFAOYSA-N 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 5
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 5
- 229910003002 lithium salt Inorganic materials 0.000 claims description 5
- 159000000002 lithium salts Chemical class 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 4
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000004210 ether based solvent Substances 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 239000002808 molecular sieve Substances 0.000 abstract description 26
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 26
- 230000000052 comparative effect Effects 0.000 description 16
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000013538 functional additive Substances 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical group [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 2
- 239000011356 non-aqueous organic solvent Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- YBDACTXVEXNYOU-UHFFFAOYSA-N C(F)(F)(F)F.[Li] Chemical compound C(F)(F)(F)F.[Li] YBDACTXVEXNYOU-UHFFFAOYSA-N 0.000 description 1
- GPVWCGHDIGTNCE-UHFFFAOYSA-N [Fe](=S)=S.[Li] Chemical compound [Fe](=S)=S.[Li] GPVWCGHDIGTNCE-UHFFFAOYSA-N 0.000 description 1
- FBDMJGHBCPNRGF-UHFFFAOYSA-M [OH-].[Li+].[O-2].[Mn+2] Chemical compound [OH-].[Li+].[O-2].[Mn+2] FBDMJGHBCPNRGF-UHFFFAOYSA-M 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003869 coulometry Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- HNCXPJFPCAYUGJ-UHFFFAOYSA-N dilithium bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].[Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F HNCXPJFPCAYUGJ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Primary Cells (AREA)
Abstract
The invention relates to an electrolyte of a primary lithium battery and a preparation method and application thereof, wherein the electrolyte comprises an electrolyte, an organic solvent and a water removing agent; the water removing agent comprises p-toluenesulfonyl isocyanate and/or fluorine-containing isocyanate. On the premise of not using a molecular sieve, the electrolyte of the primary lithium battery is prepared by mixing the water removing agent with other components in a short time, so that the water content of the electrolyte can reach a lower level.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to an electrolyte of a primary lithium battery and a preparation method and application thereof.
Background
A primary lithium battery is a high-energy chemical primary battery, commonly known as a lithium battery. The lithium metal is used as a negative electrode, salts dissolved in an organic solvent are used as an electrolyte, and metal oxide or other solid and liquid oxidants are used as a positive active material. The primary lithium battery mainly produced at present according to the positive electrode material division has a lithium-manganese dioxide battery (Li-MnO)2) Lithium-carbon fluoride battery (Li/(CF)n) Lithium-iron disulfide battery (Li/FeS)2) And the like. The primary battery has the outstanding advantages of high specific energy, long storage life (annual self-discharge rate is less than 1 percent) and the like.
CN102107093A relates to lithium ionizationThe technical field of electrolyte of a sub-battery and discloses a method for removing water and reducing acid of the electrolyte of a lithium ion battery and a lithium type molecular sieve used in the method. The method disclosed by the invention is to adopt a molecular sieve to carry out water removal and deacidification treatment on a solvent and an additive in the lithium ion battery electrolyte, wherein the molecular sieve is a lithium type molecular sieve, namely the lithium type molecular sieve is obtained by lithiating a common molecular sieve in a lithium salt solvent. It discloses that ordinary molecular sieves such as 3A, 4A, 5A and the like are placed in Li-containing solution+In the solution, according to the ion exchange principle, the common molecular sieve is lithiated to obtain the lithium type molecular sieve, and when the lithium type molecular sieve is used for removing water and acid from the electrolyte of the lithium ion battery, the requirement of water removal can be met, and the impurity ions Na caused by ion exchange with Li & lt + & gt can be greatly reduced+、K+Etc. so as not to increase the content of other metal ions in the electrolyte.
CN107959052A discloses a lithium ion battery electrolyte for removing water and acid and improving high voltage performance, and the disclosed electrolyte comprises lithium salt, a non-aqueous organic solvent, a silazane additive and other functional additives. The lithium salt, the non-aqueous organic solvent, the silazane additive and other functional additives account for 5.0-18.0% by mass, 83.0-94.0% by mass, 0.1-5.0% by mass and 0.1-5.0% by mass of the total content of the lithium ion battery electrolyte which can remove water and reduce acid and improve high voltage performance. The preparation process is simple, the cost is low, and the implementation is easy.
The existing common water removal method is to remove water by using a 3A, 4A or 5A molecular sieve, but the time required for removing water by using the molecular sieve is long (generally several hours to tens of hours), and in addition, the discarded molecular sieve can also have adverse effects on the environment.
In view of the above, it is important to develop an electrolyte for a primary lithium battery that is environmentally friendly and has a low water content.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide an electrolyte of a primary lithium battery, a preparation method and application thereof, wherein the electrolyte is environment-friendly and has low water content.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an electrolyte for a primary lithium battery, the electrolyte comprising an electrolyte, an organic solvent and a water scavenger;
the water removing agent comprises p-toluenesulfonyl isocyanate and/or fluorine-containing isocyanate.
The electrolyte of the primary lithium battery comprises the water removing agent of a specific type, so that the water content of the electrolyte can be kept at a low level on the premise of not using a molecular sieve.
Preferably, the molar ratio of the water scavenger to water in other components of the electrolyte is (1-1.5):1, wherein 1-1.5 may be 1.01, 1.02, 1.03, 1.04, 1.05, 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, etc., preferably 1 (1.01-1.05).
The water removal agent can greatly reduce the water content in the electrolyte under the condition of less usage amount.
Preferably, the electrolyte comprises a lithium salt.
Preferably, the electrolyte comprises any one of lithium perchlorate, lithium triflate (LiTFS), lithium bistrifluoromethylsulphonylimide (LiTFSi), lithium bistrifluorosulphonylimide (LiFSi), lithium bisoxalato borate (LiBOB) or lithium difluorooxalato borate (LiODFB), or a combination of at least two thereof, wherein typical but non-limiting combinations include: combinations of lithium perchlorate and lithium trifluoromethanesulfonate, combinations of lithium trifluoromethanesulfonate, lithium bistrifluoromethylsulfonimide and lithium bisfluorosulfonimide, combinations of lithium bistrifluoromethylsulfonimide, lithium bisfluorosulfonimide, lithium bisoxalato borate and lithium difluorooxalato borate, and the like.
Preferably, the mass percentage of the electrolyte in the electrolyte is 1% -20%, such as 2%, 4%, 6%, 8%, 10%, 12%, 14%, 16%, 18%, etc., based on 100% of the total mass of the electrolyte.
Preferably, the organic solvent includes a combination of a cyclic carbonate-based organic solvent and an ether-based solvent.
Preferably, the cyclic carbonate includes Ethylene Carbonate (EC) and/or Propylene Carbonate (PC).
Preferably, the ethereal solvent comprises any one of or a combination of at least two of ethylene glycol dimethyl ether (DME), diethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, 1, 3-Dioxolane (DXL) or Tetrahydrofuran (THF), wherein typical but non-limiting combinations include: combinations of ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, combinations of diethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether and 1, 3-dioxolane, combinations of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, 1, 3-dioxolane and tetrahydrofuran, and the like.
Preferably, the mass percentage of the organic solvent in the electrolyte is 80% to 99%, such as 82%, 84%, 86%, 88%, 90%, 92%, 94%, 96%, 98%, etc., based on 100% of the total mass of the electrolyte.
In a second aspect, the present invention provides a method for preparing an electrolyte of a primary lithium battery according to the first aspect, the method comprising the steps of: and mixing the electrolyte and the organic solvent, and stirring and mixing the mixed solution and the water removal agent for 5-15min (such as 6min, 7min, 8min, 9min, 10min, 11min, 12min, 13min, 14min and the like) to obtain the electrolyte of the primary lithium battery.
In the preparation of the electrolyte, the water removal agent and other components can be mixed for a short time to remove water from the electrolyte.
Preferably, the operation of detecting the water content is performed before the mixed solution is mixed with the water removal agent.
Preferably, the operation of detecting the water content is performed after the mixed solution is mixed with the water removal agent.
Preferably, the operation of detecting the water content of the electrolyte and the organic solvent is performed independently before and after the agitation mixing.
In a third aspect, the present invention provides a primary lithium battery comprising a battery case, a cell, and the electrolyte of the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) on the premise of not using a molecular sieve, the electrolyte of the primary lithium battery is prepared by mixing the water removing agent and other components in a short time, so that the water content of the electrolyte can reach a lower level.
(2) When the water removal time is within 15min, p-toluenesulfonyl isocyanate and/or fluorine-containing isocyanate are/is used as a water removal agent, the molecular sieve amount is not discarded, and the water content after water removal is below 86 ppm;
when the water removal time is within 15min, the molar ratio of the water removal agent to water in other components of the electrolyte is (1-1.5):1, no molecular sieve is discarded, and the water content after water removal is below 25 ppm;
when the water removing agent is p-toluenesulfonyl isocyanate, the water removing time is 10min, and when the water removing agent is slightly excessive than water in other components of the electrolyte, the molar ratio of the water removing agent to the water in the other components of the electrolyte is (1-1.05): within 1 hour, the water removal effect is better, and the water content after water removal is below 18 ppm.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides an electrolyte of a primary lithium battery, which comprises an electrolyte, a water removal agent and an organic solvent, wherein the total mass of the electrolyte is 200 kg;
the electrolyte is lithium perchlorate, and the mass percent of the electrolyte in the electrolyte is 12 percent;
the water removing agent is p-toluenesulfonyl isocyanate, and the addition amount of the water removing agent in the electrolyte is 22.22 mol;
the organic solvent is PC, DME and DXL with the mass ratio of 1:1:1, and is 100% in the electrolyte.
The preparation method of the electrolyte comprises the following steps:
mixing the electrolyte and the organic solvent, detecting the total water content of the electrolyte and the organic solvent to be 2000ppm, adding the water removing agent, stirring and mixing for 10min, and continuously detecting the water content of the system.
Example 2
The embodiment provides an electrolyte of a primary lithium battery, which comprises an electrolyte, a water removal agent and an organic solvent, wherein the total mass of the electrolyte is 200 kg;
the electrolyte is lithium bis (fluorosulfonyl) imide, and the mass percentage of the electrolyte in the electrolyte is 12%;
the water removing agent is p-toluenesulfonyl isocyanate, and the addition amount of the water removing agent in the electrolyte is 22.44 mol;
the organic solvent is PC, DME and DXL with the mass ratio of 1:1:1, and is 100% in the electrolyte.
The preparation method of the electrolyte comprises the following steps:
mixing the electrolyte and the organic solvent, detecting the total water content of the electrolyte and the organic solvent to be 2000ppm, adding the water removing agent, stirring and mixing for 10min, and continuously detecting the water content of the system.
Example 3
The embodiment provides an electrolyte of a primary lithium battery, which comprises an electrolyte, a water removal agent and an organic solvent, wherein the total mass of the electrolyte is 200 kg;
the electrolyte is lithium perchlorate, and the mass percent of the electrolyte in the electrolyte is 12 percent;
the water removing agent is p-toluenesulfonyl isocyanate, and the addition amount of the water removing agent in the electrolyte is 22.66 mol;
the organic solvent is PC, DME and DXL with the mass ratio of 1:1:1, and is 100% in the electrolyte.
The preparation method of the electrolyte comprises the following steps:
mixing the electrolyte and the organic solvent, detecting the total water content of the electrolyte and the organic solvent to be 2000ppm, adding the water removing agent, stirring and mixing for 10min, and continuously detecting the water content of the system.
Examples 4 to 10
Examples 4 to 10 are different from example 1 in that the amount of the water scavenger added was 22.89mol (example 4), 22.11mol (example 5), 23.33mol (example 6), 21.99mol (example 7), 21.78mol (example 8), 33.33mol (example 9) and 35.552mol (example 10), respectively, and the rest was the same as example 1.
Example 11
The embodiment provides an electrolyte of a primary lithium battery, which comprises an electrolyte, a water removal agent and an organic solvent, wherein the total mass of the electrolyte is 200 kg;
the electrolyte is lithium trifluoromethanesulfonate and lithium bis-trifluoromethanesulfonimide in a mass ratio of 1:1, and the mass percentage of the electrolyte is 1%;
the water removing agent is
The adding amount of the electrolyte is 22.22 mol;
the organic solvent is EC, diethylene glycol dimethyl ether and tetrahydrofuran in a mass ratio of 1:2:1, and the organic solvent is 100% in the electrolyte.
The preparation method of the electrolyte comprises the following steps:
mixing the electrolyte and the organic solvent, detecting the total water content of the electrolyte and the organic solvent to be 2000ppm, adding the water removing agent, stirring and mixing for 5min, and continuously detecting the water content of the system.
Example 12
The embodiment provides an electrolyte of a primary lithium battery, which comprises an electrolyte, a water removal agent and an organic solvent, wherein the total mass of the electrolyte is 200 kg;
the electrolyte is composed of lithium bis (fluorosulfonyl) imide, lithium bis (oxalato) borate and lithium difluoro (oxalato) borate in a mass ratio of 1:1:2, and the mass percentage of the electrolyte in the electrolyte is 20%;
the water removing agent is 1:2 in mass ratio
And p-toluenesulfonyl isocyanate, the addition amount in the electrolyte is 22.44 mol;
the organic solvent is EC and ethylene glycol methyl ethyl ether with the mass ratio of 1:2, and the organic solvent is 100% in the electrolyte.
The preparation method of the electrolyte comprises the following steps:
mixing the electrolyte and the organic solvent, detecting the total water content of the electrolyte and the organic solvent to be 2000ppm, adding the water removing agent, stirring and mixing for 15min, and continuously detecting the water content of the system.
Comparative examples 1 to 4
This comparative example differs from example 1 in that it does not contain a water scavenger, and was prepared by mixing an electrolyte with an organic solvent and drying the mixture for 720 minutes using a 2kg, 4A molecular sieve, the remainder being the same as example 1.
Comparative examples 2 to 4
The present comparative example and comparative example 1 are distinguished by replacing 2kg, 4A molecular sieve with 6kg, 4A molecular sieve (comparative example 2), 8kg, 4A molecular sieve (comparative example 3) and 10kg, 4A molecular sieve (comparative example 4), respectively, with the remainder being the same as in comparative example 1.
Comparative example 5
This comparative example differs from example 1 in that p-toluenesulfonyl isocyanate was replaced with an equal amount of hexamethyldisilazane and the remainder was the same as in example 1.
Performance testing
The electrolytes described in examples 1 to 12 and comparative examples 1 to 5 were subjected to a water content test by: karl Fischer coulometry.
The test results are summarized in table 1.
TABLE 1
As can be seen from the analysis of the data in Table 1, the examples show that when the water removal time is within 15min, p-toluenesulfonyl isocyanate and/or fluorine-containing isocyanate are/is used as the water removal agent, the molecular sieve amount is not discarded, and the water content after water removal is below 86 ppm; when the water removal time is within 15min, the molar ratio of the water removal agent to water in other components of the electrolyte is (1-1.5):1, no molecular sieve is discarded, and the water content after water removal is below 25 ppm; when the water removing agent is preferably p-toluenesulfonyl isocyanate, the water removing time is 10min, and when the water removing agent is slightly excessive than water in other components of the electrolyte, the molar ratio of the water removing agent to the water in the other components of the electrolyte is (1-1.05): within 1 hour, the water removal effect is better, and the water content after water removal is below 18 ppm. The electrolyte disclosed by the invention does not need to be dried by using a molecular sieve, and the electrolyte with lower water content is formed in a shorter dehydration time.
As can be seen from the analysis of comparative examples 1 to 4 and example 1, comparative examples 1 to 4 are inferior to example 1 in performance, and it is proved that the electrolyte obtained by adding the water scavenger to the electrolyte is better in performance.
As can be seen from the analysis of comparative example 5 and example 1, the performance of comparative example 5 is inferior to that of example 1, and the water content of the electrolyte formed by the water scavenger of the invention is lower.
As can be seen from the analysis of examples 7-10 and example 1, examples 7-8 are inferior to examples 1 and 9, and example 10 is superior in water removal effect, but the amount of the water removing agent needs to be increased, which results in an excessively high cost, and thus the molar ratio of the water removing agent to water is proved to be lower in the range of 1 (1-1.5) to form the electrolyte.
The present invention is illustrated in detail by the examples described above, but the present invention is not limited to the details described above, i.e., it is not intended that the present invention be implemented by relying on the details described above. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The electrolyte of a primary lithium battery is characterized by comprising an electrolyte, an organic solvent and a water removal agent;
the water removing agent comprises p-toluenesulfonyl isocyanate and/or fluorine-containing isocyanate.
2. The electrolyte for a primary lithium battery according to claim 1, wherein the molar ratio of the water scavenger to water in other components of the electrolyte is (1-1.5): 1.
3. The electrolyte for a primary lithium battery according to claim 1 or 2, wherein the electrolyte comprises a lithium salt;
preferably, the electrolyte comprises any one of lithium perchlorate, lithium trifluoromethanesulfonate, lithium bistrifluoromethylsulfonimide, lithium bistrifluorosulfonimide, lithium bisoxalato borate or lithium difluorooxalato borate or a combination of at least two thereof.
4. The electrolyte for a primary lithium battery according to any one of claims 1 to 3, wherein the mass percentage of the electrolyte in the electrolyte is 1 to 20% based on 100% by mass of the total mass of the electrolyte.
5. The electrolyte for a primary lithium battery according to any one of claims 1 to 4, wherein the organic solvent comprises a combination of a cyclic carbonate-based organic solvent and an ether-based solvent.
6. The electrolyte for a primary lithium battery according to any one of claims 1 to 5, wherein the cyclic carbonate comprises ethylene carbonate and/or propylene carbonate;
preferably, the ether solvent includes any one of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, 1, 3-dioxolane or tetrahydrofuran, or a combination of at least two thereof.
7. The electrolyte for a primary lithium battery according to any one of claims 1 to 6, wherein the organic solvent is contained in the electrolyte in an amount of 80 to 99% by mass based on 100% by mass of the total mass of the electrolyte.
8. A method of preparing an electrolyte for a primary lithium battery according to any one of claims 1 to 7, characterized in that the method comprises the steps of: and mixing the electrolyte and the organic solvent, and stirring and mixing the mixed solution and the water removal agent for 5-15min to obtain the electrolyte of the primary lithium battery.
9. The preparation method according to claim 8, characterized in that the operation of detecting the water content is performed before the mixed solution is mixed with the water removing agent;
preferably, the operation of detecting the water content is performed after the mixed solution is mixed with the water removal agent.
10. A primary lithium battery comprising a battery casing, a cell, and the electrolyte of any one of claims 1-7.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111086731.9A CN113851666A (en) | 2021-09-16 | 2021-09-16 | Electrolyte of primary lithium battery and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111086731.9A CN113851666A (en) | 2021-09-16 | 2021-09-16 | Electrolyte of primary lithium battery and preparation method and application thereof |
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| WO2024104049A1 (en) * | 2022-11-14 | 2024-05-23 | 合肥国轩高科动力能源有限公司 | Electrolyte and lithium ion battery |
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Application publication date: 20211228 |