CN106785040B - 1,3,5,2,4,6- tri- oxygen trithian -2,2, the preparation method of 4,4,6,6- hexoides - Google Patents
1,3,5,2,4,6- tri- oxygen trithian -2,2, the preparation method of 4,4,6,6- hexoides Download PDFInfo
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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Abstract
1,3,5,2,4,6- tri- oxygen trithians -2,2,4, the preparation method of 4,6,6- hexoides belongs to the technical field of compound, with 1,3,5,2,4,6- tri- oxygen trithians are raw material, and methylene chloride is solvent, under the conditions of existing for the catalyst, oxidation reaction directly occurs with oxidant, control reaction temperature is -15 DEG C~15 DEG C, then reaction time 0.5h-10h passes through liquid separation, organic phase dehydration, is concentrated to get 1,3,5,2,4, tri- oxygen trithian -2,2 of 6-, 4,4,6,6- hexoides.Preparation method of the present invention is simple, and by the strict control to method, reaction process is stable, mild, and the 1,3 of preparation, 5,2,4,6- tri- oxygen trithians -2,2,4,4,6,6- hexoides are applied to good application effect in electrolyte, considerably increase the cycle performance and service life of battery.
Description
Technical field
The invention belongs to the technical fields of compound, are related to the preparation of oxa- thiophene alkane, and in particular to 1,3,5,2,4,6- tri-
The preparation method of oxygen trithian -2,2,4,4,6,6- hexoide.
Background technique
Tri- oxygen trithian -2,2,4,4,6,6- hexoide of 1,3,5,2,4,6- is lithium-ion battery electrolytes
Additive, No. CAS is 13771-24-9, molecular formula O9S3, molecular weight 240.19.Tri- oxygen trithio heterocycle of 1,3,5,2,4,6-
Hexane -2,2, additive of 4,4,6, the 6- hexoides as lithium-ion battery electrolytes, preparation method or synthesis technology mesh
Preceding report is extremely fresh rare, for 1,3,5,2,4,6- tri- oxygen trithian -2,2 of synthesis of how simple safety, 4,4,6,
6- hexoide is current urgent problem.
Summary of the invention
The object of the present invention is to provide a kind of tri- oxygen trithian -2,2,4,4,6,6- six of 1,3,5,2,4,6- oxidations
The preparation method of object, as novel electrolysis additive, so that the high temperature cyclic performance (especially 622/ of ternary battery
The ternary battery of 811 types) it is more preferable.
The present invention be realize its purpose the technical solution adopted is that:
1,3,5,2,4,6- tri- oxygen trithian -2,2, the preparation method of 4,4,6,6- hexoides, with 1,3,5,
2,4,6- tri- oxygen trithians are raw material, and methylene chloride is solvent, direct with oxidant under the conditions of existing for the catalyst
Oxidation reaction occurs, control reaction temperature is -15 DEG C~15 DEG C, reaction time 0.5h-10h, then de- by liquid separation, organic phase
Water is concentrated to get tri- oxygen trithian -2,2,4,4,6,6- hexoide of 1,3,5,2,4,6-.
The molar ratio of tri- oxygen trithian of 1,3,5,2,4,6- and oxidant is 1:(1.6-8).
The dosage of catalyst is the 0.03%-3% of tri- oxygen trithian quality of 1,3,5,2,4,6-.
The oxidant is one or more mixtures of sodium hypochlorite, hydrogen peroxide, potassium permanganate.
The catalyst is the mixing of one or both of ruthenium trichloride, ruthenium-oxide.
Oxidant carries out oxidation reaction with 1,3,5,2,4,6- tri- oxygen trithians in such a way that dropwise addition or stream add,
Controlling the time that oxidant is added dropwise or stream adds is 0.4-0.6h.
Carbonic acid two is added into obtained tri- oxygen trithian -2,2,4,4,6,6- hexoide of 1,3,5,2,4,6-
Methyl esters is recrystallized, 1 refined, 3,5,2,4,6- tri- oxygen trithians -2,2,4,4,6,6- hexoides.
The beneficial effects of the present invention are:
The present invention newly devises a kind of lithium ion battery additive, so that the high temperature cyclic performance of ternary battery is (especially
The ternary battery of 622/811 type) it is more preferable.It joined tri- oxygen trithian -2,2,4,4,6,6- of 1,3,5,2,4,6-, six oxygen
Anode can be effectively protected in compound, reduce dissolution of the transition metal on positive electrode, while can form SEI in cathode
Film inhibits deposition and reduction of the transition metal on cathode, so that cathode is effectively protected, i.e., 1,3,5,2,4,6- tri- oxygen trithios
Azacyclohexane -2,2 while anode is protected in the addition of 4,4,6,6- hexoides again, can also realize protection cathode；Be conducive to
Improve battery stable circulation performance under high voltages and high temperature cyclic performance；And caused by effectively lithium battery being prevented to overcharge
The generation of the safety problems such as on fire, explosion, increases the safety of battery；Charge and discharge is high-efficient, good cycle, is able to satisfy 45 DEG C
Under the conditions of with 600 capacity retention ratios of 1C charge and discharge cycles greater than 85% charge and discharge requirement, can especially improve the height of lithium battery
Warm cycle performance；The storge quality of battery can be increased, do not influence other performances of lithium battery.
The molecular formula of tri- oxygen trithian of 1,3,5,2,4,6- is O3S3, molecular weight 144, chemical structural formula is as follows:
1,3,5,2,4,6- tri- oxygen trithian -2,2, No. CAS of 4,4,6,6- hexoides are 13771-24-9,
Chemical structural formula is as follows:
Specific embodiment
The present invention is further illustrated combined with specific embodiments below.
One, specific embodiment
Embodiment 1
Tri- oxygen trithian of 1,3,5,2,4,6- is added in the four-hole boiling flask equipped with blender thermometer condenser pipe
14.4g (0.1mol), methylene chloride 100g, ruthenium trichloride 0.1g start that 10% sodium hypochlorite 177.6g is added dropwise at -15 DEG C
(0.24mol), 0.5h is dripped off, and in -15 DEG C of insulation reaction 1h, after reaction liquid separation.Organic phase dehydration, is concentrated to dryness, and obtains
To 1,3,5,2,4,6- tri- oxygen trithian -2,2,4,4,6,6- hexoides, to further increase 1,3,5,2,4,6-
Three oxygen trithians -2,2, the purity of 4,4,6,6- hexoides are added 200gDMC and are recrystallized, obtains product
7.2g, yield 75%.
Embodiment 2
Tri- oxygen trithian of 1,3,5,2,4,6- is added in the four-hole boiling flask equipped with blender thermometer condenser pipe
14.4g (0.1mol), methylene chloride 100g, ruthenium sesquioxide 0.1g start that 30% hydrogen peroxide 68g is added dropwise at -5 DEG C
(0.6mol), 0.5h is dripped off, -5 DEG C of insulation reaction 3h, liquid separation after reaction.Organic phase dehydration, is concentrated to dryness, and is added
200gDMC is recrystallized, and product 14.2g is obtained.Yield 59.1%.
Embodiment 3
Tri- oxygen trithian of 1,3,5,2,4,6- is added in the four-hole boiling flask equipped with blender thermometer condenser pipe
14.4g (0.1mol), methylene chloride 100g, ruthenium sesquioxide 0.1g start that 30% hydrogen peroxide 90.6g is added dropwise at -5 DEG C
(0.8mol), 0.5h is dripped off, -5 DEG C of insulation reaction 5h, liquid separation after reaction.Organic phase dehydration, is concentrated to dryness, and is added
200gDMC is recrystallized, and product 17.6g, yield 73.3% are obtained.
Embodiment 4
Tri- oxygen trithian of 1,3,5,2,4,6- is added in the four-hole boiling flask equipped with blender thermometer condenser pipe
14.4g (0.1mol), methylene chloride 100g, ruthenium trichloride 0.1g start that 10% sodium hypochlorite 595.2g is added dropwise at 0 DEG C
(0.8mol), 0.5h is dripped off, 0 DEG C of insulation reaction 6h, liquid separation after reaction.Organic phase dehydration, is concentrated to dryness, and is added
200gDMC is recrystallized, and product 21.3g, yield 88.75% are obtained.
Embodiment 5
Tri- oxygen trithian of 1,3,5,2,4,6- is added in the four-hole boiling flask equipped with blender thermometer condenser pipe
It is anti-that potassium permanganate 52.2g (0.33mol) is added at 15 DEG C in 14.4g (0.1mol), methylene chloride 100g, ruthenium sesquioxide 0.14g
10h to be answered, is filtered after reaction, organic phase dehydration is concentrated to dryness, and 200gDMC is added and is recrystallized, product 13.3g is obtained,
Yield 55.4%.
Embodiment 6
Tri- oxygen trithian of 1,3,5,2,4,6- is added in the four-hole boiling flask equipped with blender thermometer condenser pipe
14.4g (0.1mol), methylene chloride 100g, ruthenium trichloride 0.015g start that 10% sodium hypochlorite 296g is added dropwise at 0 DEG C
(0.4mol), 0.4h is dripped off, 0 DEG C of insulation reaction 4h, liquid separation after reaction.Organic phase dehydration, is concentrated to dryness, and is added
200gDMC is recrystallized, and product 11.2g, yield 70% are obtained.
Embodiment 7
Tri- oxygen trithian of 1,3,5,2,4,6- is added in the four-hole boiling flask equipped with blender thermometer condenser pipe
14.4g (0.1mol), methylene chloride 100g, ruthenium trichloride 0.05g start that 10% sodium hypochlorite 118.4g is added dropwise at 0 DEG C
(0.16mol), 0.6h is dripped off, 0 DEG C of insulation reaction 7h, liquid separation after reaction.Organic phase dehydration, is concentrated to dryness, and is added
200gDMC is recrystallized, and product 4.6g, yield 72% are obtained.
Two, concrete application effect
Add using tri- oxygen trithian -2,2,4,4,6,6- hexoide of 1,3,5,2,4,6- of the present invention as additive
Enter into high-voltage lithium-ion battery electrolyte, then will after the electrolyte assembled battery carry out performance cycle test, while with
The battery of electrolyte, the other additive electrolyte of addition that functional additive is not added carries out performance comparison.It is specific as follows:
Electrolyte 1: addition tri- oxygen trithian -2,2,4,4,6,6- hexoide of 1,3,5,2,4,6- of the present invention；
Electrolyte 2: additivated electrolyte is not added；
Electrolyte 3: fluoro- 1,3 propene sultone of addition 3- or -1,3 propene sultone of 3- cyano；
Electrolyte 4: adding other additives, for example, propenyl-1,3-sulfonic acid lactone and/or vinylethylene carbonate or
Lithium-containing compound LiN (the C of person's vinylene carbonate (VC), sulfimide classxF2x+1SO2)(CyF2y+1SO2) (wherein, x, y are
Positive integer) and fluoro 1,3- propane sultone etc..
Using ternary material NCM (622) lithium as positive electrode, cathode uses carbonaceous mesophase spherules, the distribution of positive and negative anodes collector
For aluminium foil and copper foil, diaphragm forms soft-package battery using ceramic diaphragm, and after injecting electrolyte, Soft Roll electricity is assembled into glove box
Pond is tested after standing 8 hours.Charge and discharge pair are carried out with 1/10C 3.0V to 4.5V or more respectively under 25 DEG C of constant temperature of room temperature
Battery is activated, and then circulation under the conditions of 45 DEG C is with 1C charge and discharge.Loop test the results are shown in Table 1.
Table 1
Battery discharge conservation rate under different multiplying: by battery with 0.5C constant-current discharge to 3.0V, shelving 5min, then with
0.5C constant-current charge is to 4.5V or more, and constant-voltage charge, is 0.05C by electric current, stands 5min, then respectively with 0.2C, 1C,
1.5C, 2C constant-current discharge are to by voltage 3.0V.Discharge capacity under the conditions of record 0.2C, 1C, 1.5C, 2C is D1, record
Discharge capacity under 0.2C is D0, and based on the discharge capacity under 0.2C, passes through discharge capacitance=[(D1- of battery
D0)/D0] × 100% formula is calculated discharge capacitance of the battery under different multiplying and (surveys 15 batteries, take it
Average value), discharge capacitance of each battery under 25 DEG C of conditions, different multiplying is as shown in table 2.
Table 2
The evaluation of battery high-temperature storge quality: the test of 60 DEG C/7D and 85 DEG C/7D storage performance, following table 3 is that battery handles mark
After quasi- charge and discharge again 60 DEG C storage 7 days and 85 DEG C store 7 days, then measurement battery capacity retention ratio and capacity restoration rate.
Table 3
Battery low-temperature storage performance evaluation；The following table 4 is that battery is shelved in cryogenic box, respectively controlled at -30 DEG C
Or -40 DEG C, time 240min is shelved, the capacity retention ratio of battery is then measured.
Table 4
Hot tank test: battery carries out following tests:
1) battery is charged to by 4.5V or more with the constant current of 1.0C electric current, then constant-voltage charge to electric current is down to 0.05C, charging
Stop；2) battery is placed in hot tank, is started to warm up from 25 DEG C to 180 DEG C with the heating rate of 5 DEG C/min, after reaching 180 DEG C
It remains temperature-resistant, then starts timing, the state of battery is observed after 1h, passes through the standard of the test are as follows: battery is without smoldering, nothing
It is on fire, no explosion, wherein every group of 5 batteries.The results are shown in Table 5 for the hot tank test of each battery.It is surveyed by above-mentioned hot tank
Examination, characterizes the security performance of battery.
Table 5
| Project | State after hot tank test |
| Electrolyte 1 | 5 batteries pass through, and do not smolder, is on fire, explosion phenomenon |
| Electrolyte 2 | 3 batteries are smoldered, 2 battery catches fires |
| Electrolyte 3 | 4 batteries pass through, and 1 battery is smoldered |
| Electrolyte 4 | 2 batteries pass through, and 2 batteries are smoldered, 1 battery catches fire |
Claims (7)
1.1,3,5,2,4,6- tri- oxygen trithians -2,2, the preparation method of 4,4,6,6- hexoides, which is characterized in that with 1,
3,5,2,4,6- tri- oxygen trithians are raw material, the chemical structural formula of described 1,3,5,2,4,6- tri- oxygen trithians
ForMethylene chloride is solvent, and under the conditions of existing for the catalyst, oxidation reaction directly occurs with oxidant, is controlled
Reaction temperature processed is -15 DEG C~15 DEG C, reaction time 0.5h-10h, then passes through liquid separation, organic phase dehydration, is concentrated to get 1,3,
5,2,4,6- tri- oxygen trithians -2,2,4,4,6,6- hexoides, described 1,3,5,2,4,6- tri- oxygen trithio heterocycles oneself
The chemical structural formula of alkane -2,2,4,4,6,6- hexoide is
2. tri- oxygen trithian -2,2,4,4,6,6- hexoide of 1,3,5,2,4,6- according to claim 1
Preparation method, which is characterized in that the molar ratio of 1,3,5,2,4,6- tri- oxygen trithian and oxidant is 1:(1.6-8).
3. tri- oxygen trithian -2,2,4,4,6,6- hexoide of 1,3,5,2,4,6- according to claim 1
Preparation method, which is characterized in that the dosage of catalyst is the 0.03%-3% of 1,3,5,2,4,6- tri- oxygen trithian quality.
4. tri- oxygen trithian -2,2,4,4,6,6- hexoide of 1,3,5,2,4,6- according to claim 1
Preparation method, which is characterized in that the oxidant is the mixing of one or more of sodium hypochlorite, hydrogen peroxide, potassium permanganate
Object.
5. tri- oxygen trithian -2,2,4,4,6,6- hexoide of 1,3,5,2,4,6- according to claim 1
Preparation method, which is characterized in that the catalyst is the mixing of one or both of ruthenium trichloride, ruthenium-oxide.
6. tri- oxygen trithian -2,2,4,4,6,6- hexoide of 1,3,5,2,4,6- according to claim 1
Preparation method, which is characterized in that oxidant carries out in such a way that dropwise addition or stream add with 1,3,5,2,4,6- tri- oxygen trithians
Oxidation reaction, the time that control oxidant is added dropwise or stream adds are 0.4-0.6h.
7. tri- oxygen trithian -2,2,4,4,6,6- hexoide of 1,3,5,2,4,6- according to claim 1
Preparation method, which is characterized in that 1 obtained, 3,5,2,4,6- tri- oxygen trithians -2,2, in 4,4,6,6- hexoides plus
Enter dimethyl carbonate to be recrystallized, 1 refined, 3,5,2,4,6- tri- oxygen trithians -2,2,4,4,6,6- six
Oxide.
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| CN103328464A (en) * | 2010-10-29 | 2013-09-25 | Ktp有限公司 | Method for preparing 1,3,5-trioxane |
| CN105837554A (en) * | 2016-05-06 | 2016-08-10 | 河北科技大学 | Synthesis method for 1,3,5-trithio heterocyclic hexane derivative |
| WO2016156599A1 (en) * | 2015-04-02 | 2016-10-06 | Universiteit Leiden | Electrocatalysts for efficient water electrolysis |
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2016
- 2016-12-27 CN CN201611226427.9A patent/CN106785040B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103328464A (en) * | 2010-10-29 | 2013-09-25 | Ktp有限公司 | Method for preparing 1,3,5-trioxane |
| WO2016156599A1 (en) * | 2015-04-02 | 2016-10-06 | Universiteit Leiden | Electrocatalysts for efficient water electrolysis |
| CN105837554A (en) * | 2016-05-06 | 2016-08-10 | 河北科技大学 | Synthesis method for 1,3,5-trithio heterocyclic hexane derivative |
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| Dimers, trimers and oligomers of sulfur oxides: an ab initio and;C. Groves, E. Lewars;《Journal of Molecular Structure》;19991004;全文 * |
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