CN104617333B - A kind of nonaqueous electrolytic solution and lithium rechargeable battery - Google Patents
A kind of nonaqueous electrolytic solution and lithium rechargeable battery Download PDFInfo
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- CN104617333B CN104617333B CN201510004643.8A CN201510004643A CN104617333B CN 104617333 B CN104617333 B CN 104617333B CN 201510004643 A CN201510004643 A CN 201510004643A CN 104617333 B CN104617333 B CN 104617333B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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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- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention discloses a kind of nonaqueous electrolytic solution and lithium rechargeable battery, the nonaqueous electrolytic solution includes non-aqueous organic solvent, lithium salts and following (A) and (B)：(A) the pyrovinic acid acid anhydride shown in structural formula 1；(B) at least one compound of the vinyl ethylene carbonate compound selected from the vinylene carbonate ester compounds shown in structural formula 2, the mesomethylene carbon acetate compounds shown in structural formula 3, shown in structural formula 4；Wherein, in structural formula 2,3,4, R1~R12It is each independently selected from the alkyl that hydrogen atom, halogen or carbon number are 1~5.The nonaqueous electrolytic solution of the present invention is used in lithium rechargeable battery, on the one hand good SEI films can be formed in GND, on the other hand battery impedance can be reduced, so that lithium rechargeable battery has good charge/discharge cycle characteristics and cryogenic property and high-temperature storage performance.
Description
Technical field
The present invention relates to lithium-ion battery electrolytes technical field, it can be used for lithium ion two more specifically to one kind
Nonaqueous electrolytic solution in primary cell and the lithium rechargeable battery using the nonaqueous electrolytic solution.
Background technology
Lithium ion battery is compared with other batteries, and with light weight, small volume, operating voltage is high, energy density is high, output
Power is big, charge efficiency is high, memory-less effect and the advantages of have extended cycle life, and 3C batteries and power vehicle are had become at present
The first choice of battery.Past 10 years, the steady growth of 3C batteries drove the fast development of lithium battery industry.The lithium in 3C fields from
Sub- secondary cell, it is desirable to specific energy density is high, cycle performance and the characteristics of good high-temperature behavior；And in power vehicle field,
Power lithium-ion battery requirement has excellent high temperature performance, long-life cycle performance, longer-term storage performance and security performance
The characteristics of.
Cobalt acid lithium material Yin Qigao specific energy density and good cycle performance, is always 3C fields lithium ion battery
Preferred positive electrode, but shortcoming of the cobalt acid lithium as positive electrode is that its security is poor, and price is high.Ternary nickel cobalt manganese material and
LiFePO 4 material is because of the main flow positive electrode of its excellent cycle performance and security as current driving force lithium ion battery；Three
First material power lithium-ion battery has energy density high, and normal temperature circulation and cryogenic property are excellent, the good advantage of security, shortcoming
It is that high-temperature behavior is not enough；LiFePO 4 material power lithium-ion battery has that cycle performance and high-temperature behavior are excellent, and security is excellent
Different advantage, has the disadvantage that cryogenic property is not enough, energy density is relatively low.No matter for which kind of material lithium ion battery, electrolyte
It is to influence the key factor of the every chemical property of battery, especially, the additive in electrolyte is sent out the properties of battery
Wave and be even more important.
Current 3C fields generally use cobalt acid lithium battery, and more and more use high voltage cobalt acid lithium battery.
As the energy density of lithium ion battery requires to improve constantly, battery increasingly requires high capacity, this require battery just,
Negative pole surface density and compacted density are improved constantly, and what is brought therewith is exactly that the impedance of battery constantly increases.
And in power lithium-ion battery field, in order to ensure that carbonic acid can be typically selected in excellent cycle performance, electrolyte
Vinylene (VC), mesomethylene carbon vinyl acetate or vinyl ethylene carbonate etc. are used as film for additive.Because this three class adds
Plus agent is in battery initial charge, excellent SEI films can be formed in graphite cathode, the SEI films compactness is good, and heat endurance is good,
Reduction decomposition of the electrolyte in negative pole can substantially be suppressed, the stability of negative pole in cyclic process is substantially increased, so as to carry significantly
Cycle life under the high cycle life of battery, particularly high temperature.But this kind of film for additive is when in use, also there is obvious
Shortcoming, is exactly that the formed SEI membrane impedances of its decomposition are larger, directly results in increase and the low temperature of battery DC internal resistance (DCIR)
The obvious deterioration of performance, and the two performances can become apparent from the raising of film for additive content, deterioration.Therefore, in power
In battery, improved using additives such as vinylene carbonate (VC), mesomethylene carbon vinyl acetate and vinyl ethylene carbonates
While circulation, the problem of solving the high impedance that these additives are brought.
The high impedance and electrokinetic cell field electrolyte brought to solve the problems, such as the small battery core in 3C fields because of high power capacity because
The high impedance problem brought using VC, mesomethylene carbon vinyl acetate, vinyl ethylene carbonate etc. is, it is necessary in the two fields
Battery electrolyte system in use low-impedance additive can drop.Using reduction impedance additive in electrolyte, it can reduce
DCIR in the impedance of battery, reduction charge and discharge process, improves cryogenic property, high-temperature behavior and cycle performance.
The content of the invention
The present invention provide it is a kind of can be used for lithium rechargeable battery in nonaqueous electrolytic solution, the normal temperature of the nonaqueous electrolytic solution and
High temperature cyclic performance is excellent, impedance is relatively low, cryogenic property and high-temperature behavior are good；And on this basis should there is provided a kind of use
The lithium rechargeable battery of nonaqueous electrolytic solution, it has excellent combination property.
According to the first aspect of the invention, the present invention provides a kind of lithium rechargeable battery nonaqueous electrolytic solution, comprising non-aqueous
Organic solvent, lithium salts, also comprising following (A) and (B)：
(A) the pyrovinic acid acid anhydride shown in structural formula 1；
(B) selected from the vinylene carbonate ester compounds shown in structural formula 2, the mesomethylene carbon vinyl acetate shown in structural formula 3
At least one compound of vinyl ethylene carbonate compound shown in compound, structural formula 4；
Wherein, in structural formula 2,3,4, R1~R12It is 1~5 to be each independently selected from hydrogen atom, halogen or carbon number
Alkyl.
As the preferred scheme of the present invention, (A) accounts for the 0.1%-5% of electrolyte gross weight.
As the preferred scheme of the present invention, (B) accounts for the 0.2%-5% of electrolyte gross weight.
As the preferred scheme of the present invention, the gross weight and (B) that (A) accounts for electrolyte are accounted between the gross weight of electrolyte
Ratio be more than or equal to 0.2.
As the preferred scheme of the present invention, (B) is vinylene carbonate, mesomethylene carbon vinyl acetate and vinyl carbon
At least one of vinyl acetate compound.
It is used as the preferred scheme of the present invention, in addition to PS, Isosorbide-5-Nitrae-butane sultone and 1,3- propylene sulphur
At least one of lactone compound.
As the preferred scheme of the present invention, the non-aqueous organic solvent is selected from ethylene carbonate, propene carbonate, carbonic acid fourth
It is more than one or both of alkene ester, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and methyl propyl carbonate.
As the preferred scheme of the present invention, the lithium salts is selected from lithium hexafluoro phosphate, lithium perchlorate, LiBF4, double fluorine
It is more than Lithium bis (oxalate) borate, two (trimethyl fluoride sulfonyl) one or both of imine lithiums and imidodisulfuryl fluoride lithium salt.
According to the second aspect of the invention, the present invention provides a kind of lithium rechargeable battery, including positive pole, negative pole and is placed in
Barrier film between positive pole and negative pole, in addition to the nonaqueous electrolytic solution described in first aspect.
As the preferred scheme of the present invention, the structural formula of the active material of the positive pole is selected from：
LiNixCoyMnzL(1-x-y-z)O2, wherein, 0.2≤x≤0.8,0≤y≤0.8,0≤z≤0.8, L be Al, Sr, Mg,
Ti, Ca, Zr, Zn, Si or Fe；Or LiFexMn1-xPO4, wherein, 0<x≤1；Or LiCoxM1-xO2, wherein, 0<X≤1, M be Al,
Sr, Mg, Ti, Ca, Zr, Zn, Si or Fe.
Contain pyrovinic acid acid anhydride in the nonaqueous electrolytic solution of the present invention, can be in negative pole formation SEI films, and formed
SEI membrane impedances are relatively low, it is ensured that lithium ion battery obtains excellent cryogenic property and high-temperature behavior；VC, methylene in electrolyte
Ethylene carbonate or vinyl ethylene carbonate etc. can form excellent SEI films in negative pole, it is ensured that lithium ion battery obtains excellent
Good normal temperature and high temperature cyclic performance, therefore the nonaqueous electrolytic solution of the present invention has the cyclicity for making lithium ion battery acquisition excellent
Energy, relatively low impedance, the beneficial effect of excellent cryogenic property and high-temperature behavior.
It is important to note that in Application No. CN200610088591.8 patent, electricity is used as using sulphonic acid anhydride
Use of the solution additive in 4.35V ternary nickel cobalt manganese cells is solved, used sulphonic acid anhydride is butane sulphonic acid anhydride and butane pentane
Sulphonic acid anhydride, it is indicated that their effect is the inside aerogenesis for suppressing battery, improves the high-temperature behavior of battery.In addition, in the patent No.
Have in JP3760539 and should be particularly mentioned that sulfonic acid anhydride additive can be effectively formed SEI films, suppress decomposition of the electrolyte in negative pole,
Improve the cycle performance of battery.The sulphonic acid anhydride referred in these patents is typically all to be used to improve high-temperature behavior and cycle performance,
Sulphonic acid anhydride is not mentioned to and drops low-impedance effect, does not more refer to using pyrovinic acid acid anhydride reducing impedance, improving battery
The case of performance.The present invention with patent CN200610088591.8 and JP3760539 except that, be novelty selection
Pyrovinic acid acid anhydride reduces battery impedance as lithium battery electrolytes additive, and in the allied substances of sulphonic acid anhydride, only
Pyrovinic acid acid anhydride has the effect of reduction battery impedance, because the organic group of pyrovinic acid acid anhydride is minimum.First is used in electrolyte
Base sulphonic acid anhydride can not only reduce battery impedance as additive, but also improve the high temperature performance and cycle performance of battery,
Particularly high temperature cyclic performance.
Embodiment
To make the purpose of the present invention, content and effect of greater clarity, below by way of embodiment to the present invention
It is described in detail.
The present invention's it is critical that inventor, which adds pyrovinic acid acid anhydride, contains the non-aqueous of the additives such as vinylene carbonate
After in electrolyte, it is surprised to find that pyrovinic acid acid anhydride can significantly decrease the battery brought by additives such as vinylene carbonates
The problem of impedance is higher.That is, inventor is by the way that the additives such as pyrovinic acid acid anhydride and vinylene carbonate are applied in combination,
The nonaqueous electrolytic solution of battery impedance can be reduced by being made a kind of, while guarantee battery excellent cycle performance, be obtained excellent
Cryogenic property and high-temperature behavior.
Nonaqueous electrolytic solution in one embodiment of the invention, includes non-aqueous organic solvent, lithium salts and following compound
And (B) (A)：
(A) the pyrovinic acid acid anhydride shown in structural formula 1；
(B) selected from the vinylene carbonate ester compounds shown in structural formula 2, the mesomethylene carbon vinyl acetate shown in structural formula 3
At least one of vinyl ethylene carbonate compound shown in compound and structural formula 4 compound；
Wherein, in structural formula 2,3,4, R1~R12It is 1~5 to be each independently selected from hydrogen atom, halogen or carbon number
Alkyl.
Preferably, above-claimed cpd (B) is vinylene carbonate, mesomethylene carbon vinyl acetate and vinyl ethylene carbonate
At least one of compound.
Above-claimed cpd (B) is commonly used in form the additive of SEI films in nonaqueous electrolytic solution, and their addition can be carried
High cycle performance of battery, especially high temperature cyclic performance, but the formed SEI membrane impedances of its decomposition are larger, directly results in
The overall impedance increase of battery, so as to cause the obvious deterioration of cryogenic property and rate charge-discharge performance.And in the present invention, addition
Pyrovinic acid acid anhydride can reduce impedance, improve cryogenic property and high-temperature behavior.
In the preferred embodiment of the present invention, the pyrovinic acid acid anhydride shown in structural formula 1 accounts for electrolyte gross weight
0.1%~5%, when pyrovinic acid acid anhydride content is less than 0.1%, film-formation result is poor, it is impossible to effectively reduce battery impedance；And work as
When content is more than 5%, the SEI films formed in negative pole are thicker, can increase battery impedance, deterioration on the contrary.
In the preferred embodiment of the present invention, compound (B) accounts for the 0.2%~5% of electrolyte gross weight.Working as
It is relatively thin in the SEI films of negative pole formation when the content of compound (B) is less than 0.2%, not fine and close enough, the self-regeneration in cyclic process
Ability is poor, and due improvement result is not had to circulation；When content is more than 5%, the impedance of battery can be significantly increased, and be caused
The cryogenic property severe exacerbation of battery.
In the preferred embodiment of the present invention, compound (A) accounts for the gross weight of electrolyte and compound (B) accounts for electricity
The ratio solved between the gross weight of liquid is more than or equal to 0.2.When ratio is less than 0.2, illustrate that the content of pyrovinic acid acid anhydride is relatively low, it is right
Reduction impedance does not have due improvement, does not just have due improve to improving cryogenic property and high-temperature behavior yet and imitates
Really.But in general ratio is unsuitable too high, if the too high content that may illustrate compound (B) is not enough, cause in negative pole shape
Into SEI films it is relatively thin, not fine and close enough, self-repairing capability is poor in cyclic process, and due improve is not had to circulation and is made
With.
In the preferred embodiment of the present invention, PS, Isosorbide-5-Nitrae-fourth are also included in nonaqueous electrolytic solution
It is more than one or both of alkane sultone and 1,3- propene sultones.These compounds typically have in positive and negative electrode film forming
Effect, can effectively suppress the inflatable after battery high-temperature storage, improve high-temperature behavior.
Non-aqueous organic solvent in the present invention, selected from ethylene carbonate, propene carbonate, butylene, carbonic acid diformazan
It is more than one or both of ester, diethyl carbonate, methyl ethyl carbonate and methyl propyl carbonate.
Lithium salts electrolyte in the present invention, selected from lithium hexafluoro phosphate, lithium perchlorate, LiBF4, double fluorine oxalic acid boric acid
It is more than lithium, two (trimethyl fluoride sulfonyl) one or both of imine lithiums and imidodisulfuryl fluoride lithium salt.
In the present invention, the active material of lithium ion secondary battery positive electrode is selected from：
LiNixCoyMnzL(1-x-y-z)O2, wherein, 0.2≤x≤0.8,0≤y≤0.8,0≤z≤0.8, L be Al, Sr, Mg,
Ti, Ca, Zr, Zn, Si or Fe, such as LiNi1/3Mn1/3Co1/3O2、LiNi0.5Mn0.3Co0.2O2、LiNi0.8Mn0.1Co0.1O2Deng excellent
Elect LiNi as1/3Mn1/3Co1/3O2；Or LiFexMn1-xPO4, wherein, 0<X≤1, preferably LiFePO4；Or LiCoxM1-xO2, its
In, 0<X≤1, M is Al, Sr, Mg, Ti, Ca, Zr, Zn, Si or Fe, preferably LiCoO2。
The present invention is more specifically explained below by specific embodiment and comparative example, these embodiments and right
Ratio is not limiting the scope of the invention.
Embodiment 1
It is prepared by the preparation method of the present embodiment lithium ion battery, including positive pole preparation process, negative pole preparation process, electrolyte
Step, barrier film preparation process and battery number of assembling steps.
The positive pole preparation process is：By 96.8:2.0:1.2 quality is than blended anode active material LiNi1/3Mn1/ 3Co1/3O2, conductive carbon black and binding agent polyvinylidene fluoride, be dispersed in METHYLPYRROLIDONE, obtain anode sizing agent, will
Anode sizing agent is uniformly coated on the two sides of aluminium foil, by drying, calendering and is dried in vacuo, and aluminum of being burn-on with supersonic welder
Positive plate is obtained after lead-out wire, the thickness of pole plate is between 120-150 μm.
The negative pole preparation process is：By 96:1:1.2:1.8 quality is than admixed graphite, conductive carbon black, binding agent butylbenzene
Rubber and carboxymethyl cellulose, disperse in deionized water, to obtain cathode size, cathode size is coated on to the two sides of copper foil
On, by drying, calendering and it is dried in vacuo, and burn-on with supersonic welder and obtain negative plate, the thickness of pole plate after nickel lead-out wire
Degree is between 120-150 μm.
The electrolyte preparation process is：It is EC by volume by ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate:
EMC:DMC=3:3:4 are mixed, and the lithium hexafluoro phosphate that concentration is 1.1mol/L is added after mixing, are added total based on electrolyte
The 0.2wt% of weight vinylene carbonate and 0.1wt% pyrovinic acid acid anhydride.
The barrier film preparation process is：Using polypropylene, three layers of barrier film of polyethylene and polypropylene, thickness is 20 μm.
Battery number of assembling steps is：Three layers of barrier film that thickness is 20 μm are placed between positive plate and negative plate, then will
The sandwich structure of positive plate, negative plate and barrier film composition is wound, then is put into square aluminum metal after coiling body is flattened
In shell, the lead-out wire of both positive and negative polarity is respectively welded on the relevant position of cover plate, and with laser-beam welding machine by cover plate and metal-back
It is welded as a whole, obtains treating the battery core of fluid injection；The electrolyte of above-mentioned preparation is injected in battery core by liquid injection hole, the amount of electrolyte
Ensure the space being full of in battery core.
Then the conventional chemical conversion of initial charge is carried out according to the following steps：0.05C constant-current charges 3min, 0.2C constant-current charge
5min, 0.5C constant-current charge 25min, shelve 1hr, and then shaping, after-teeming liquid, sealing is further filled with 0.2C electric current constant current
Electricity is to 4.2V, after normal temperature shelf 24hr, 0.2C constant-current constant-voltage chargings to 4.2V, then with 0.2C electric current constant-current discharge extremely
3.0V。
1) high temperature cyclic performance is tested：It is at 45 DEG C, the battery after chemical conversion is permanent with 1C for ternary and cobalt acid lithium battery
Stream constant pressure is charged to 4.2V, then with 1C constant-current discharges to 3.0V.For ferric phosphate lithium cell, at 60 DEG C, by the electricity after chemical conversion
Pond is charged to 3.6V with 1C constant current constant voltages, then with 1C constant-current discharges to 2.0V.Calculate the 500th time and follow after 500 circulations of charge/discharge
The conservation rate of ring capacity.Calculation formula is as follows：
500th circulation volume conservation rate (%)=(the 500th cyclic discharge capacity/first time cyclic discharge capacity) ×
100%；
2) normal-temperature circulating performance is tested：At 25 DEG C, the battery after chemical conversion is charged to 4.2V (for phosphorus with 1C constant current constant voltages
Sour lithium iron battery, is charged to 3.6V), then (for ferric phosphate lithium cell, put with 1C constant-current discharges to 3.0V to 2.0V).Discharge charge
The conservation rate of the 500th circulation volume is calculated after 500 circulations of electricity.Calculation formula is as follows：
500th circulation volume conservation rate (%)=(the 500th cyclic discharge capacity/first time cyclic discharge capacity) ×
100%；
3) high-temperature storage performance：Battery after chemical conversion is full of with 1C constant current constant voltages at normal temperatures, measurement battery is initially put
Capacitance, then after 60 DEG C store 30 days, 3.0V (for ferric phosphate lithium cell, putting to 2.0V), measurement electricity are discharged to 1C
The holding capacity and recovery capacity in pond.Calculation formula is as follows：
Battery capacity conservation rate (%)=holding capacity/initial capacity × 100%；
Capacity resuming rate (%)=recovery capacity/initial capacity × 100%.
4) low temperature performance is tested：At 25 DEG C, the battery after chemical conversion is charged to 4.2V (for phosphorus with 1C constant current constant voltages
Sour lithium iron battery, is charged to 3.6V), then (for ferric phosphate lithium cell, put with 1C constant-current discharges to 3.0V to 2.0V), record is put
Capacitance.Then 1C constant current constant voltages are full of, and are shelved in the environment for being placed in -20 DEG C after 12h, and 1C constant-current discharges to 3.0V are (for phosphorus
Sour lithium iron battery, puts to 2.0V), record discharge capacity.
- 20 DEG C of low temperature discharging efficiency value=1C discharge capacities (- 20 DEG C)/1C discharge capacities (25 DEG C).
5) often low temperature DCIR performance tests：At 25 DEG C, the battery 1C after chemical conversion is charged to half electricity condition, used respectively
0.1C, 0.2C, 0.5C, 1C and 2C charge and discharge ten seconds, records discharge and recharge blanking voltage respectively；The battery of half electricity condition is placed in -10
At DEG C, respectively with 0.1C, 0.2C and 0.5C charge and discharges ten seconds record discharge and recharge blanking voltage respectively.Then, filling with different multiplying
Discharge current is abscissa (unit：A), using the blanking voltage corresponding to charging and discharging currents as ordinate, linear relationship chart is done (single
Position：mV).
DCIR values=difference the charging current that charges and the slope value of the linear graph of corresponding blanking voltage.
The slope value of electric discharge DCIR values=difference discharge current and the linear graph of corresponding blanking voltage.
Embodiment 2-18
In embodiment 2-18, except additive composition, content (being based on electrolyte gross weight) and positive electrode are as shown in table 1
Outside, it is other same as Example 1.Table 1 is each composition content table of electrolysis additive and different tertiary cathode materials.
Table 1
Comparative example 1-6
In comparative example 1-6, in addition to additive composition and content (being based on electrolyte gross weight) are pressed and added shown in table 2, its
It is same as Example 1.Table 2 is each component content table of electrolysis additive.
Table 2
Embodiment 1-18 and comparative example 1-6 performance comparison
Table 3 is embodiment 1-18 and comparative example 1-6 performance comparison table.
Table 3
Contrasted by embodiment 1-18 with comparative example 1-6, it can be found that after addition pyrovinic acid acid anhydride, can not only carry
High high-temperature behavior, and substantially reduce the impedance under impedance, particularly low temperature.It is also possible to find, pyrovinic acid acid anhydride and carbon
Sour vinylene (VC), mesomethylene carbon vinyl acetate and vinyl ethylene carbonate are respectively combined after use, the cyclicity of battery
Can, particularly high temperature cyclic performance performance is more excellent, and cryogenic property is also significantly improved, in particular for high-temperature storage
Performance, improvement is suitable with the combination of vinylene carbonate (VC) and PS (PS).
Embodiment 19-32
In embodiment 19-32, except in battery preparation method by positive electrode active materials LiNi1/3Mn1/3Co1/3O2Change into
Lithium iron phosphate positive material LiFePO4, each additive composition and content (being based on electrolyte gross weight) of electrolyte are as shown in table 4
It is other same as Example 1 outside addition.Table 4 is each component weight content of embodiment 19-32 electrolysis additive
Table.
Table 4
Comparative example 7-12
In comparative example 7-12, except in battery preparation method by positive electrode active materials LiNi1/3Mn1/3Co1/3O2Change phosphorus into
Sour iron lithium anode material LiFePO4, additive composition and content (being based on electrolyte gross weight) are pressed shown in table 5 outside addition, other
It is same as Example 1.Table 5 is each component content table of electrolysis additive.
Table 5
Embodiment 19-32 and comparative example 7-12 performance
Table 6 is embodiment 19-32 and comparative example 7-12 performance comparison table.
Table 6
Contrasted by embodiment 19-32 with comparative example 7-12, it can be found that after addition pyrovinic acid acid anhydride, not only can be with
High-temperature behavior is improved, and substantially reduces the impedance under impedance, particularly low temperature.It is also possible to find, pyrovinic acid acid anhydride with
Vinylene carbonate (VC), mesomethylene carbon vinyl acetate and vinyl ethylene carbonate are respectively combined after use, and cryogenic property is obtained
To being obviously improved, the high-temperature behavior and cycle performance of battery also show more excellent, in particular for high temperature circulation, improve effect
Fruit is more excellent than the combination of vinylene carbonate (VC) and 1,3- the third disulfonic acid acid anhydrides.
Embodiment 33-46
In embodiment 33-46, except in battery preparation method by positive electrode active materials LiNi1/3Mn1/3Co1/3O2Change into
Positive electrode LiCoO2, outside each additive composition and content (being based on electrolyte gross weight) of electrolyte shown in table 7 by adding,
It is other same as Example 1.Table 7 is each component weight content table of embodiment 33-46 electrolysis additive.
Table 7
Comparative example 13-18
In comparative example 13-18, except in battery preparation method by positive electrode active materials LiNi1/3Mn1/3Co1/3O2Change into
Positive electrode LiCoO2, additive composition is outer by addition shown in table 8 with content (be based on electrolyte gross weight), it is other with implementation
Example 1 is identical.Table 8 is each component content table of electrolysis additive.
Table 8
Embodiment 33-46 and comparative example 13-18 performance comparison
Table 9 is embodiment 33-46 and comparative example 13-18 performance comparison table.
Table 9
Contrasted by embodiment 33-46 with comparative example 13-18, it can be found that after addition pyrovinic acid acid anhydride, not only may be used
To improve high-temperature behavior, and substantially reduce the impedance under impedance, particularly low temperature.It is also possible to find, pyrovinic acid acid anhydride
It is respectively combined with vinylene carbonate (VC), mesomethylene carbon vinyl acetate and vinyl ethylene carbonate after use, the height of battery
Warm nature can be improved with cycle performance.
In summary, in the electrolysis additive for the lithium ion battery that the present invention is provided, by adding vinylene carbonate
Class compound, mesomethylene carbon vinyl acetate class compound or vinyl ethylene carbonate class compound, further add methyl sulphur
Acid anhydrides, while ensureing that battery obtains excellent cycle performance, can be effectively improved the cryogenic property and high-temperature storage of battery
Performance.Further, it is also possible to further add the additives such as 1,3- propane sultones so that properties more optimize.
Above content is to combine specific embodiment further description made for the present invention, it is impossible to assert this hair
Bright specific implementation is confined to these explanations.For general technical staff of the technical field of the invention, do not taking off
On the premise of from present inventive concept, some simple deduction or replace can also be made.
Claims (9)
1. a kind of lithium rechargeable battery nonaqueous electrolytic solution, includes non-aqueous organic solvent, lithium salts, it is characterised in that also comprising with
Under (A) and (B)：
(A) the pyrovinic acid acid anhydride shown in structural formula 1；
(B) the mesomethylene carbon acetate compounds shown in structural formula 3；
Wherein, in structural formula 3, R3~R6It is each independently selected from the alkyl that hydrogen atom, halogen or carbon number are 1~5；
(A) accounts for the 0.1%-5% of electrolyte gross weight；
(B) accounts for the 0.2%-5% of electrolyte gross weight.
2. nonaqueous electrolytic solution according to claim 1, it is characterised in that (B) also includes：Selected from shown in structural formula 2
Vinylene carbonate ester compounds and/or structural formula 4 shown in vinyl ethylene carbonate compound；
Wherein, R1、R2、R7~R12It is each independently selected from the alkyl that hydrogen atom, halogen or carbon number are 1~5.
3. nonaqueous electrolytic solution according to claim 1 or 2, it is characterised in that (A) account for the gross weight of electrolyte with
(B) ratio accounted between the gross weight of electrolyte is more than or equal to 0.2.
4. nonaqueous electrolytic solution according to claim 1 or 2, it is characterised in that (B) is vinylene carbonate, methylene
At least one of base ethylene carbonate and vinyl ethylene carbonate compound.
5. nonaqueous electrolytic solution according to claim 1 or 2, it is characterised in that also including PS, Isosorbide-5-Nitrae-fourth
At least one of alkane sultone and 1,3- propene sultones compound.
6. nonaqueous electrolytic solution according to claim 1 or 2, it is characterised in that the non-aqueous organic solvent is selected from ethylene
One in alkene ester, propene carbonate, butylene, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and methyl propyl carbonate
Plant or two or more.
7. nonaqueous electrolytic solution according to claim 1 or 2, it is characterised in that the lithium salts is selected from lithium hexafluoro phosphate, high chlorine
One in sour lithium, LiBF4, double fluorine Lithium bis (oxalate) borates, two (trimethyl fluoride sulfonyl) imine lithiums and imidodisulfuryl fluoride lithium salt
Plant or two or more.
8. a kind of lithium rechargeable battery, including positive pole, negative pole and the barrier film that is placed between positive pole and negative pole, it is characterised in that
Also include the nonaqueous electrolytic solution described in claim any one of 1-7.
9. lithium rechargeable battery according to claim 8, it is characterised in that the structural formula of the active material of the positive pole
It is selected from：
LiNixCoyMnzL(1-x-y-z)O2, wherein, 0.2≤x≤0.8,0≤y≤0.8,0≤z≤0.8, L be Al, Sr, Mg, Ti,
Ca, Zr, Zn, Si or Fe；Or LiFexMn1-xPO4, wherein, 0<x≤1；Or LiCoxM1-xO2, wherein, 0<X≤1, M be Al, Sr,
Mg, Ti, Ca, Zr, Zn, Si or Fe.
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| CN201510004643.8A CN104617333B (en) | 2015-01-05 | 2015-01-05 | A kind of nonaqueous electrolytic solution and lithium rechargeable battery |
| PCT/CN2015/089149 WO2016110123A1 (en) | 2015-01-05 | 2015-09-08 | Non-aqueous electrolyte and lithium ion secondary battery |
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| CN201510004643.8A CN104617333B (en) | 2015-01-05 | 2015-01-05 | A kind of nonaqueous electrolytic solution and lithium rechargeable battery |
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| CN104617333B (en) * | 2015-01-05 | 2017-10-24 | 深圳新宙邦科技股份有限公司 | A kind of nonaqueous electrolytic solution and lithium rechargeable battery |
| CN106299324A (en) * | 2016-10-17 | 2017-01-04 | 广州天赐高新材料股份有限公司 | A kind of electrolyte for high-capacity lithium ion cell, preparation method and lithium ion battery |
| EP3528332B1 (en) * | 2017-03-17 | 2021-06-02 | LG Chem, Ltd. | Electrolyte for lithium secondary battery and lithium secondary battery comprising same |
| CN109088099B (en) * | 2018-06-28 | 2021-01-26 | 华南师范大学 | Sulfonyl electrolyte additive giving consideration to high and low temperature performance and electrolyte containing additive |
| CN110661028B (en) * | 2018-06-29 | 2021-04-09 | 深圳新宙邦科技股份有限公司 | Lithium ion battery non-aqueous electrolyte and lithium ion battery |
| CN110265721B (en) * | 2018-09-19 | 2021-03-30 | 宁德时代新能源科技股份有限公司 | Lithium ion secondary battery |
| CN109860709B (en) * | 2019-01-11 | 2020-12-11 | 杉杉新材料（衢州）有限公司 | Electrolyte for improving low-temperature performance of lithium ion battery and lithium ion battery containing electrolyte |
| CN112216864B (en) * | 2019-07-09 | 2024-03-22 | 宁德时代新能源科技股份有限公司 | Lithium ion battery |
| CN112310483B (en) * | 2019-07-30 | 2021-09-17 | 宁德时代新能源科技股份有限公司 | Lithium ion battery |
| CN111200162A (en) * | 2019-12-06 | 2020-05-26 | 联动天翼新能源有限公司 | Lithium ion battery electrolyte and preparation method thereof |
| ES2940776T3 (en) * | 2019-12-24 | 2023-05-11 | Contemporary Amperex Technology Co Ltd | Secondary battery and device comprising the secondary battery |
| CN110994027B (en) * | 2019-12-25 | 2022-05-13 | 湖州昆仑亿恩科电池材料有限公司 | Lithium ion battery electrolyte with good high-temperature cycle characteristic and lithium ion battery |
| CN113889665A (en) * | 2020-07-02 | 2022-01-04 | 浙江蓝天环保高科技股份有限公司 | Water removal additive, electrolyte containing water removal additive and lithium ion battery |
| CN112467222B (en) * | 2020-10-23 | 2022-09-16 | 福建南平延平区南孚新能源科技有限公司 | Button secondary battery |
| CN112259791A (en) * | 2020-10-27 | 2021-01-22 | 惠州亿纬锂能股份有限公司 | Non-aqueous electrolyte, preparation method thereof and lithium ion battery |
| CN114024033B (en) * | 2020-12-30 | 2024-10-18 | 珠海冠宇电池股份有限公司 | Nonaqueous electrolyte for lithium ion battery and lithium ion battery comprising same |
| CN112968157B (en) * | 2021-02-06 | 2022-11-01 | 苏州精诚智造智能科技有限公司 | Preparation method of power lithium ion battery |
| CN113851637A (en) * | 2021-08-23 | 2021-12-28 | 合肥国轩高科动力能源有限公司 | Polyfunctional group electrolyte additive, electrolyte containing additive and lithium ion battery |
| CN114335740B (en) * | 2021-12-29 | 2023-07-28 | 湖北亿纬动力有限公司 | Formation method of lithium ion battery and lithium ion battery |
| CN114566633A (en) * | 2022-03-04 | 2022-05-31 | 中化国际(控股)股份有限公司 | Novel cobalt-free cathode material and preparation method thereof |
| CN116315064B (en) * | 2023-01-17 | 2024-10-01 | 南开大学 | Solid polymer electrolyte and preparation method of battery thereof |
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Effective date of registration: 20190108 Address after: 215000 No. 15, East Suhong Road, Suzhou Industrial Park, Suzhou City, Jiangsu Province Patentee after: Noel battery material (Suzhou) Co., Ltd. Address before: 518118 Shatuo Tongfu Industrial Zone, Pingshan New District, Shenzhen City, Guangdong Province Patentee before: Shenzhen Xinyubang Science and Technology Co., Ltd. |