CN113540563A - Additive and modification method of lithium battery electrolyte - Google Patents
Additive and modification method of lithium battery electrolyte Download PDFInfo
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- CN113540563A CN113540563A CN202010305428.2A CN202010305428A CN113540563A CN 113540563 A CN113540563 A CN 113540563A CN 202010305428 A CN202010305428 A CN 202010305428A CN 113540563 A CN113540563 A CN 113540563A
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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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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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Abstract
The invention provides an electrolyte for a lithium battery, wherein the electrolyte contains an organic solvent, a lithium salt and an additive, and the additive is obtained from the following components: a protic ionic liquid component; and NH3Preparing components; and said NH3The molar ratio of the ionic liquid to the proton type ionic liquid is (0.01-7): 1. the invention also provides a preparation method and application of the corresponding lithium battery electrolyte, and a lithium battery containing the lithium battery electrolyte.
Description
Technical Field
The invention belongs to the field of battery additives, and particularly relates to an additive for a lithium battery, a modification method of electrolyte for the lithium battery and a preparation method of the additive.
Background
As a new generation of energy storage technology, lithium ion batteries have the characteristics of high energy density, good cycle performance, large specific power and the like, can be used in the fields of portable electronic equipment, electric automobiles, power grid peak shaving, small standby power stations and the like, and are increasingly paid attention to by people. The lithium ion battery is composed of a positive electrode material, a negative electrode material (pole core), electrolyte, a diaphragm and the like, wherein the electrolyte is called lithium battery 'blood' and is a migration medium of lithium ions and a bridge for connecting the positive electrode and the negative electrode, and has very important influence on the cycle life, the safety performance, the working temperature, the rate performance, the reversible capacity and the like of the battery.
The ideal electrolyte has wide electrochemical stability window, wide working temperature range (-30-80 ℃), no reaction with each element in the battery, high lithium ion transmission rate and good charge-discharge cycle performance. At present, the electrolyte of a commercial lithium ion battery is mainly a compound solution based on a carbonate organic solvent and a lithium salt, and various additives are added to improve the performance of the electrolyte, but the electrolyte has the problems of easy volatilization, flammability, narrow use temperature range, safety accidents caused by overcharging and the like, and the electrolyte hinders the development of the lithium battery in the fields of power batteries and the like.
The Ionic Liquids (ILs) are salts composed of anions and cations and are liquid at room temperature, have the excellent characteristics of good thermal stability, low steam pressure, non-volatility, non-flammability, wide liquid temperature range, high Ionic conductivity, stable chemical property and the like, and show good application prospects in the aspect of lithium battery electrolyte application. The ionic liquid is added into the electrolyte as an additive, so that the dissolution and ionization of the electrolyte to lithium ions can be improved, the volatility of the electrolyte is reduced, and the flame retardant property of the electrolyte is improved. In addition, ionic liquids include protic ionic liquids and aprotic ionic liquids, and the protic ionic liquids in the prior art are considered to be inapplicable to lithium batteries due to the problem of proton corrosion thereof. This greatly limits the use of ionic liquids in lithium batteries. In addition, the mass ratio of the ionic liquid as the additive in the electrolyte is usually less than 30%, because the ionic liquid has a relatively high viscosity, and the addition of the ionic liquid additive in an excessive amount may adversely cause a decrease in the lithium ion conductivity.
Therefore, in view of the above, there is a long-standing problem in the art that a proton-type ionic liquid with excellent performance cannot or is difficult to apply to a lithium battery, and therefore, a solution to the problem of modifying the electrolyte of a lithium battery in the prior art is needed, so that the proton-type ionic liquid in the prior art can also be applied to the lithium battery.
Disclosure of Invention
The invention aims to solve the technical problem of providing a modified additive of electrolyte for improving the performance of a battery and simultaneously maintaining the service life of a lithium battery.
The invention also provides a modification application of the additive in the electrolyte for the lithium battery.
The invention aims to solve the third technical problem of providing the electrolyte which can improve the performance of the battery and simultaneously can keep the service life of the lithium battery.
The fourth technical problem to be solved by the invention is to provide a preparation method of the electrolyte for the lithium battery.
The fifth technical problem to be solved by the invention is to provide the application of the electrolyte for the lithium battery.
The sixth technical problem to be solved by the invention is to provide a battery containing the electrolyte.
In order to solve one of the above technical problems, a first aspect of the present invention provides an additive for an electrolyte for a lithium battery, the additive being obtained from a composition comprising:
a protic ionic liquid component; and
NH3preparing components;
and said NH3The molar ratio of the ionic liquid to the proton type ionic liquid is (0.01-7): 1.
preferably, the proton type ionic liquid is selected from imidazole proton type ionic liquid, pyridine proton type ionic liquid, piperidine proton type ionic liquid, pyrrole proton type ionic liquid, piperazine proton type ionic liquid, quaternary amine proton type ionic liquid, pyrrolidine proton type ionic liquid or a combination thereof.
More preferably, the cation of the proton type ionic liquid is any one or combination of the following structures:
in the formulae (I) to (VII), R1And R2Each independently is H or alkyl with 1-12 carbon atoms, and at least one is-H; the R is3～R9H or an alkyl group having 1 to 12 carbon atoms.
More preferably, the anion of the protic ionic liquid is selected from: cl-、Br-、I-、BF4 -、PF6 -、NO3 -、 ClO4 -、HSO3 -、HSO4 -、H2PO4 -、CH3COO-、CH3(CH2)nCOO-、SCN-、SbF6 -、AsF6 -、 CF3 -、CF3COO-、CH3SO4 -、C2H6SO4 -、C8H17SO4 -、C4F9SO3 -、CF3(CF2)nSO3 -、 (CF3SO2)3C-、(C2F5SO2)2N-、(CF3SO2)2N-、CH3CH(OH)COO-One or more of dodecyl sulfonate, benzene sulfonate and p-toluene sulfonate, wherein n is independently selected from 0-12.
Preferably, the additive is a proton type ionic liquid and NH3And (4) compounding to obtain the product.
More specifically, the additive is proton type ionic liquid-NH3And (4) compounding the solution.
The "compounding" method may be any method that allows the proton-type ionic liquid-NH3A method of forming a homogeneous solution or a heterogeneous mixture, and the resulting additive does not affect the inventive objects of the present invention.
In particular, the NH3The form of the component is ammonia or liquid ammonia or any form which does not impose a limitation on the object of the invention.
In one embodiment of the present invention, in the additive component, the protic ionic liquid component is reacted with NH3Hydrogen bonds are formed between the components.
Preferably, the protic ionic liquid component and NH3The components are acted in the form of hydrogen bonds.
More specifically, the protic ionic liquid component and NH3Complete or partial hydrogen bonds are formed between the components.
The number of the "partial hydrogen bonds" is not limited as long as it does not limit the object of the present invention.
In one embodiment of the present invention, the protic ionic liquid is synthesized by a one-step method.
More preferably, in the one-step method, the proton-type ionic liquid is prepared by performing acid-base neutralization reaction on an acid corresponding to an anion and imidazole, pyridine, piperidine, pyrrole, piperazine, quaternary amine or pyrrolidine organic substances.
In one embodiment of the invention, the protic ionic liquid is synthesized by a two-step method.
Preferably, when the anion of the protic ionic liquid is Cl-、Br-Or I-When the anion is not the same, the proton type ionic liquid is synthesized by adopting a two-step method; in the two-step method, the first step comprises the step of carrying out acid-base neutralization by adopting acids corresponding to anions and imidazole, pyridine, piperidine, pyrrole, piperazine, quaternary amine or pyrrolidine organic mattersAnd reacting to obtain a salt; and the second step comprises the step of carrying out anion exchange on the salt obtained in the first step to obtain the proton type ionic liquid.
Preferably, when the anion of the protic ionic liquid is Cl-、Br-Or I-Then the proton type ionic liquid obtained by the two-step method is subjected to anion exchange with corresponding salt to obtain Cl as an anion-、Br-Or I-The proton type ionic liquid of (1).
In order to solve the second technical problem, the second aspect of the present invention provides a use of an additive in an electrolyte for a lithium battery, which is used for modification of the electrolyte for a lithium battery.
In order to solve the third technical problem, the third aspect of the present invention provides an electrolyte for a lithium battery, which contains an organic solvent, a lithium salt and an additive.
In one embodiment of the present invention, the electrolyte contains the following components:
10-80 parts by weight of an organic solvent,
5 to 70 parts by weight of a lithium salt, and
1-80 parts of additive.
Preferably, the mass fraction of the organic solvent is 10-80%, the mass fraction of the lithium salt is 5-70%, and the mass fraction of the additive is 1-80% based on the total weight of the electrolyte.
In a specific embodiment of the present invention, the organic solvent is selected from one or more of chain acid esters and cyclic acid esters.
Preferably, the chain acid ester is selected from a fluorine-containing chain organic ester, a sulfur-containing chain organic ester, an unsaturated bond-containing chain organic ester, or a combination thereof; more preferably, the chain acid ester is selected from dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propyl methyl carbonate, dipropyl carbonate or a combination thereof.
Preferably, the cyclic acid ester is selected from a fluorine-containing cyclic organic ester, a sulfur-containing cyclic organic ester, or an unsaturated bond-containing cyclic organic ester, or a combination thereof; more preferably, the cyclic acid ester is selected from ethylene carbonate, propylene carbonate, vinylene carbonate, gamma-butyrolactone, sultone, or combinations thereof.
Preferably, the chain acid ester is selected from a fluorine-containing cyclic organic ester, a sulfur-containing cyclic organic ester, an unsaturated bond-containing cyclic organic ester, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propyl methyl carbonate, dipropyl carbonate, or a combination thereof.
In one embodiment of the invention, the lithium salt is selected from lithium tetrafluoroborate, lithium hexafluorophosphate, lithium perchlorate, lithium hexafluoroarsenate, lithium halides, lithium chloroaluminate, lithium bistrifluoromethanesulfonylimide, lithium bisfluorosulfonylimide, lithium dioxalate borate or combinations thereof.
In order to solve the fourth technical problem, a fourth aspect of the present invention provides a preparation method of the additive for an electrolyte for a lithium battery, comprising the following steps:
providing an organic solvent, a lithium salt, and an additive, wherein the additive is derived from components comprising: proton type ionic liquid component and NH3Preparing components; and said NH3The molar ratio of the ionic liquid to the proton type ionic liquid is (0.01-7): 1;
the components are mixed to obtain the electrolyte for the lithium battery.
Preferably, the proton type ionic liquid is synthesized by adopting a one-step method. Specifically, the compound is prepared by reacting an acid corresponding to an anion with imidazole, pyridine, piperidine, pyrrole, piperazine and quaternary ammonium organic matters.
Preferably, the anion is Cl-、Br-、I-Besides, the proton type ionic liquid is synthesized by adopting a two-step method.
Preferably, the anion used is Cl-、Br-、I-The proton type ionic liquid and the corresponding salt are prepared by an anion exchange method.
In order to solve the fifth technical problem, a fifth aspect of the present invention provides a use of an electrolyte for a lithium battery in the lithium battery, wherein the electrolyte contains an organic solvent, a lithium salt, and an additive, and the additive is obtained from a composition comprising:
a protic ionic liquid component; and
NH3preparing components;
and said NH3The molar ratio of the ionic liquid to the proton type ionic liquid is (0.01-7): 1.
in order to solve the sixth technical problem, according to a sixth aspect of the present invention, there is provided a lithium battery comprising a pole core and the electrolyte of the present invention, the pole core and the electrolyte being sealed in a battery case.
Preferably, the rate capability of the lithium battery can be maintained above 80% under the 5C condition, wherein the 5C condition is a condition of five times current discharge of the lithium battery.
The invention has the technical effects that: creatively combines a proton type solvent-proton type ionic liquid which is not conventionally considered to be added into the electrolyte of the lithium battery with NH3The compound form is added into the electrolyte, and the following beneficial effects can be realized:
the safety performance of the lithium battery can be improved by adding the ionic liquid into the electrolyte, but the lithium ion transmission efficiency is reduced by adding the ionic liquid in an excessive amount because the viscosity of the ionic liquid is higher, and the NH is added into the lithium battery3The complex formulation with proton type ionic liquid can greatly reduce the viscosity of the ionic liquid, thereby improving the safety performance of the lithium battery without influencing the lithium ion transmission performance; in addition, ionic liquids and NH3The dissociation degree of lithium salt can be improved by molecules, so that the lithium ion transmission performance of the electrolyte is improved; in addition, in the using process of the lithium ion battery, the electrolyte can generate free acid, the free acid can cause the influence on the battery which is difficult to recover after being accumulated to a certain degree, and the ionic liquid-NH can be prepared in the invention3The proportion and the alkalescence of the electrolyte are controlled, so that the acid generated in the use process of the battery can be neutralized, and the service life of the battery is prolonged.
Drawings
Fig. 1 shows the results of the cycle performance test of the lithium battery of example 6 of the present invention.
Detailed Description
The inventor of the invention has extensively and deeply studied and unexpectedly found that a compound solvent of proton type ionic liquid and ammonia molecules can be used as an additive of electrolyte for a lithium battery by improving the process, and more surprisingly, the additive of the ionic liquid/small molecule system provided by the invention can obviously reduce the viscosity of the ionic liquid, simultaneously, small molecule ammonia in the system can neutralize free acid generated in the using process, and the small molecule ammonia and the free acid are cooperated to overcome the technical bias that the proton type ionic liquid can not be used in the electrolyte of the lithium battery, and more unexpectedly, the invention can obviously improve the comprehensive performance of the lithium battery and prolong the service life of the lithium battery. The present invention has been completed based on this finding.
Unless otherwise specified, various starting materials of the present invention are commercially available; or prepared according to conventional methods in the art. Unless defined or stated otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention.
Various aspects of the invention are detailed below:
definition of
As used herein, the term "alkyl", unless otherwise specified, refers to straight or branched chain alkanes containing 1 to 12 carbon atoms. Preferred are alkanes having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and most preferably 1 to 4 carbon atoms. For example, alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl.
As used herein, the term "halo", unless otherwise specified, includes chloro, bromo, or iodo.
Electrolyte for lithium battery and modified additive thereof
The invention provides an electrolyte for a lithium battery, wherein the electrolyte contains an organic solvent, a lithium salt and an additive, and the additive is obtained from the following components: a protic ionic liquid component; and NH3Preparing components; and said NH3The molar ratio of the ionic liquid to the proton type ionic liquid is (0.01-7): 1.
preferably, the addition is carried outThe additive is proton type ionic liquid and NH3And (4) compounding to obtain the product. More specifically, the additive is proton type ionic liquid-NH3And (4) compounding the solution.
The electrolyte comprises the following components: 10-80 parts of organic solvent, 5-70 parts of lithium salt and 1-80 parts of additive. More preferably, the additive is 30 to 80 parts by weight, and most preferably 30 to 50 parts by weight. Preferably, the mass fraction of the organic solvent is 10-80%, the mass fraction of the lithium salt is 5-70%, and the mass fraction of the additive is 1-80% based on the total weight of the electrolyte.
Although the additive of the present invention may be present in an amount of 1 to 80 parts by weight, the inventors have found that the additive of the present invention may be present in an amount of not less than 30% by weight, and even up to 80% by weight, in the electrolyte, without causing a decrease in the conductivity of lithium ion (e.g., 30 to 80%, 40 to 80% by weight, based on the total weight of the electrolyte).
In the above technical solution, NH3The molar ratio of the compound to the proton type ionic liquid is 0.01-7, preferably 0.3-3.
More specifically, the proton-type ionic liquid is synthesized by a one-step method or a two-step method, and the method can be specifically referred to the discussion description of the method.
Additive agent
The proton type ionic liquid is selected from imidazole proton type ionic liquid, pyridine proton type ionic liquid, piperidine proton type ionic liquid, pyrrole proton type ionic liquid, piperazine proton type ionic liquid, quaternary amine proton type ionic liquid, pyrrolidine proton type ionic liquid or a combination thereof.
Preferably, the cation of the proton type ionic liquid is any one or combination of the following structures:
in the formulae (I) to (VII), R1And R2Each independently is H or alkyl with 1-12 carbon atoms, and at least one is-H; the R is3～R9H or an alkyl group having 1 to 12 carbon atoms.
Preferably, R of formula (I) to formula (VII)1is-H, R2Is methyl, or R1Is methyl, R2is-H.
Preferably, the formula (I) to formula (VII) R3～R9preferably-H or an alkyl group having 1 to 4 carbon atoms.
Preferably, the anion of the protic ionic liquid is selected from: cl-、Br-、I-、BF4 -、PF6 -、NO3 -、 ClO4 -、HSO3 -、HSO4 -、H2PO4 -、CH3COO-、CH3(CH2)nCOO-、SCN-、SbF6 -、AsF6 -、 CF3 -、CF3COO-、CH3SO4 -、C2H6SO4 -、C8H17SO4 -、C4F9SO3 -、CF3(CF2)nSO3 -、 (CF3SO2)3C-、(C2F5SO2)2N-、(CF3SO2)2N-(i.e., Tf)2N-)、CH3CH(OH)COO-One or more of dodecyl sulfonate, benzene sulfonate and p-toluene sulfonate, wherein n is independently selected from 0-12.
Preferably, the anion is preferably BF4 -、PF6 -、CF3COO-、C4F9SO3 -、CF3(CF2)nSO3 -、 (CF3SO2)3C-、(C2F5SO2)2N-、(CF3SO2)2N-Wherein n is an integer of 0 to 12.
Among the additive components, the proton type ionic liquid component and NH3Hydrogen bonds may be formed between the components.
Preferably, the protic ionic liquid component and NH3The components are acted in the form of hydrogen bonds.
More specifically, the protic ionic liquid component and NH3Complete or partial hydrogen bonds are formed between the components.
The number of the "partial hydrogen bonds" is not limited as long as it does not limit the object of the present invention.
In the above technical scheme, the ionic liquid and NH3The interaction form is hydrogen bonding.
By way of illustration of 1-methylimidazolium chloride salt, the action is shown below:
the inventors have surprisingly found that the hydrogen bonding can make the performance of the additive as an electrolyte more excellent.
Organic solvent
The organic solvent is not particularly limited, and various "organic solvents for lithium batteries" can be used without limiting the object of the present invention.
Preferably, the organic solvent is selected from one or more of chain acid esters and cyclic acid esters.
Preferably, the chain acid ester is selected from a fluorine-containing chain organic ester, a sulfur-containing chain organic ester, an unsaturated bond-containing chain organic ester, or a combination thereof; more preferably, the chain acid ester is selected from dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propyl methyl carbonate, dipropyl carbonate or a combination thereof.
Preferably, the cyclic acid ester is selected from a fluorine-containing cyclic organic ester, a sulfur-containing cyclic organic ester, or an unsaturated bond-containing cyclic organic ester, or a combination thereof; more preferably, the cyclic acid ester is selected from ethylene carbonate, propylene carbonate, vinylene carbonate, gamma-butyrolactone, sultone, or combinations thereof.
Lithium salt
The lithium salt is not particularly limited, and various "lithium salts for lithium batteries" may be employed without limitation to the object of the present invention.
In the above technical solution, preferably, the lithium salt is at least one selected from lithium tetrafluoroborate, lithium hexafluorophosphate, lithium perchlorate, lithium hexafluoroarsenate, lithium halide, lithium chloroaluminate, lithium bistrifluoromethanesulfonylimide, and lithium dioxalate borate.
Preparation method
The preparation method of the electrolyte for the lithium battery comprises the following steps:
providing an organic solvent, a lithium salt, and an additive, wherein the additive is derived from components comprising: proton type ionic liquid component and NH3Preparing components; and said NH3The molar ratio of the ionic liquid to the proton type ionic liquid is (0.01-7): 1; the components are mixed to obtain the electrolyte for the lithium battery.
More specifically, the protic ionic liquid component is placed in a container, and then an appropriate amount of ammonia gas is introduced to a desired mass concentration, i.e., NH3The molar ratio of the ionic liquid to the proton type ionic liquid is (0.01-7): 1. the order of addition can also be interchanged without affecting the object of the invention.
In the technical scheme, the proton type ionic liquid is synthesized by adopting a one-step method or a two-step method, the one-step method adopts an acid-base neutralization method, and the two-step method is to obtain the target ionic liquid by anion exchange on the basis of the one-step method.
Preferably, the proton type ionic liquid is synthesized by adopting a one-step method. Specifically, the compound is prepared by reacting an acid corresponding to an anion with imidazole, pyridine, piperidine, pyrrole, piperazine, quaternary amine and pyrrolidine organic substances. The imidazoles, pyridines, piperidines, pyrroles, piperazines, quaternary amines, pyrrolidine organics are well known to the art (proton ionic liquids field).
Preferably, the anion is Cl-、Br-、I-Besides, the proton type ionic liquid is synthesized by adopting a two-step method.
Preferably, the anion used is Cl-、Br-、I-The proton type ionic liquid and the corresponding salt are prepared by an anion exchange method.
In the technical scheme, the proton type ionic liquid-NH3The compound solution and the concentration measurement adopt a weighing method, a proper amount of ionic liquid is taken and placed in a glass centrifuge tube with a plug, and then a proper amount of ammonia gas is introduced to the expected mass concentration.
In the technical scheme, the proton type ionic liquid-NH3The preparation process of the compound additive lithium battery electrolyte is as follows: at room temperature, under the condition of no oxygen and no water, the organic solvent, the lithium salt and the proton type ionic liquid-NH are added according to the content range3The compound solvent is mixed evenly, and the electrolyte can be prepared.
Respectively using 1-methylimidazolium chloride ([ Mim ]][Cl]) And 1-methylimidazolium bistrifluoromethylsulfonyl imide salt ([ Mim ]][NTf2]) For the sake of example:
one-step synthesis of [ Mim ] [ Cl ]: taking 1-methylimidazole to react with a small amount of hydrochloric acid under ice bath and gas protection, then continuously reacting for several hours at room temperature, removing most of water by rotary evaporation after the reaction is finished, washing for several times by using an organic solvent, removing the organic solvent by rotary evaporation to obtain a product, and then continuously drying and removing the organic solvent to obtain the product 1-methylimidazole chlorine salt.
Preferably, the molar ratio of the 1-methylimidazole to the hydrochloric acid is 1: 1.02-1.05.
Preferably, the protective gas is nitrogen or argon.
Preferably, the reaction time is greater than 6 hours at room temperature.
Preferably, the rotary evaporation temperature is 50-95 ℃.
Preferably, the organic solvent adopts any 1 or at least 2 combinations of trichloromethane, ethyl acetate, tetrahydrofuran, butyl acetate, diethyl ether, chlorobenzene, xylene, toluene or carbon tetrachloride.
Preferably, the method for drying and removing the trace organic solvent is selected from any one or a combination of at least 2 of vacuum drying, freeze drying and molecular sieve adsorption, and more preferably, the vacuum drying and the molecular sieve adsorption are combined.
Two-step Synthesis [ Mim][NTf2]: take [ Mim ]][Cl]And LiNTf2Adding proper amount of water as solvent, reacting under the protection of nitrogen or argon at room temperature for several hours, washing after completion, and then rotary steaming and drying.
In the above technical scheme, 1-methylimidazolium chloride salt [ Mim ] is preferable][Cl]With lithium bistrifluoromethanesulfonimide LiNTf2The molar ratio of (A) to (B) is 1-1.05: 1.
Preferably, the reaction time is greater than 12 hours.
Preferably, the rotary evaporation temperature is 50-95 ℃.
The washing process adopts organic solvent protection. Preferably, the organic solvent for protection is one or two of dichloromethane, chloroform, ethyl acetate, tetrahydrofuran, butyl acetate, diethyl ether, and the like.
The end of the wash was marked by no precipitation of the aqueous phase by titration with a saturated silver nitrate solution.
Preferably, the drying and water removing method is selected from any one or a combination of at least 2 of vacuum drying, freeze drying and molecular sieve water removing, and more preferably, the vacuum drying and the molecular sieve water removing are selected and combined.
The water content in the obtained ionic liquid is measured by a coulometric method moisture meter, and the halogen content in the ionic liquid synthesized by the two-step method is measured by a potentiometric titration mode. The structure of the ionic liquid is characterized by means of nuclear magnetic hydrogen spectrum, carbon spectrum and infrared spectrum.
Use of
The present invention provides a use of an additive in an electrolyte for a lithium battery, the additive consisting of a group comprisingObtaining the following components: a protic ionic liquid component; and NH3Preparing components; and said NH3The molar ratio of the ionic liquid to the proton type ionic liquid is 1: (0.01-7).
The invention also provides the use of an electrolyte for a lithium battery in a lithium battery, wherein the electrolyte comprises an organic solvent, a lithium salt and an additive, the additive being obtained from components comprising: a protic ionic liquid component; and NH3Preparing components; and said NH3The molar ratio of the ionic liquid to the proton type ionic liquid is 1: (0.01-7).
Lithium battery
The invention also provides a lithium battery which comprises a pole core and the electrolyte, wherein the pole core and the electrolyte are sealed in a battery shell.
In one embodiment, a proton-containing ionic liquid, NH, is provided3The lithium battery of the electrolyte as the additive includes a positive electrode material of a core, a negative electrode material of a core, a separator, an electrolyte, and the like. Since the present invention relates only to the improvement of the electrolyte of the lithium battery of the prior art, there is no particular limitation on other compositions and structures of the lithium battery.
In the above technical solution, the positive electrode material is selected from transition metal lithium intercalation compounds, including positive electrode active materials, binders and conductive agents, preferably, the positive electrode active material is selected from various positive electrode active materials known to those skilled in the art, and the positive electrode active material may be selected from conventional positive electrode active materials of lithium ion batteries, such as LixNi1-yCoO2(wherein x is more than or equal to 0.9 and less than or equal to 1.1, and y is more than or equal to 0 and less than or equal to 1.0), LimMn2-nBnO2(wherein B is a transition metal, m is 0.9-1.1, n is 0-1.0), Li1+ aMbMn2-bO4(wherein a is more than or equal to 0.1 and less than or equal to 0.2, b is more than or equal to 0 and less than or equal to 1.0, and M is one or more of lithium, boron, magnesium, aluminum, titanium, chromium, iron, cobalt, nickel, copper, zinc, gallium, yttrium, fluorine, iodine and sulfur).
In the above technical solution, the negative electrode material is selected from materials known to those skilled in the art, and generally, the negative electrode may include a conductive substrate and a negative electrode active material coated or filled on the conductive substrate. The conductive matrix can be selected from one or more of aluminum foil, copper foil, nickel-plated steel strip and punched steel strip. The negative active material comprises a negative active material and a binder, wherein the negative active material can be selected from one or more of natural graphite, artificial graphite, petroleum coke, organic pyrolysis carbon, mesocarbon microbeads, carbon fibers, tin alloy and silicon alloy. The adhesive can be selected from one or more of conventional adhesives of lithium ion batteries, such as polyvinyl alcohol, polytetrafluoroethylene, hydroxymethyl cellulose and styrene butadiene rubber.
In the above technical solution, the membrane material may be various membranes commonly used in the art, such as a composite membrane made by welding or bonding various production brands of modified polyethylene felt, modified polypropylene felt, ultrafine glass fiber felt, vinylon felt or nylon felt produced by various manufacturers known to those skilled in the art and a wettable polyolefin microporous membrane.
Other aspects of the invention will be apparent to those skilled in the art in view of the disclosure herein.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not specified, in the following examples are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers. Unless otherwise indicated, all parts are parts by weight, all percentages are percentages by weight, all proportions are molar ratios, and all polymer molecular weights are weight average molecular weights.
In addition, unless defined or indicated otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention.
To further illustrate the contents, essential features and significant advances of the present invention, the following comparative examples and examples are described in detail below, but not limited to the examples.
Example 1 one-step Synthesis of proton-type Ionic liquid [ Bim][NO3]：
This example is provided to illustrate the proton-type ionic liquid-NH-provided by the present invention3And (3) synthesis and preparation of a compound solvent.
(1) Firstly, calibrating the concentration of nitric acid, adding a certain amount of concentrated nitric acid into a proper amount of water for dilution, and then titrating by using a NaOH solution with over-concentration calibrated by a potassium hydrogen phthalate solution to determine the concentration of the nitric acid; (2) putting a certain amount of butylimidazole (0.1mol) into a single-neck flask, carrying out nitrogen protection, dropwise adding a calibrated equimolar amount of nitric acid into the butylimidazole through a constant-pressure funnel, carrying out magnetic stirring in an ice bath, and continuing to react for 6 hours at room temperature after dropwise addition is finished; (3) after the reaction is finished, removing water from the mixture through rotary evaporation at the temperature of 65 ℃, and then transferring the mixture to a vacuum drying oven for 24 hours at the temperature of 60 ℃; (4) extracting and washing the crude product with n-hexane for 5 times, then removing the organic solvent by rotary evaporation (50 ℃), and removing trace water and the organic solvent by vacuum drying (60 ℃, 24 hours) and low-temperature freeze drying (-20 ℃), thus obtaining a light yellow liquid product [ Bim][NO3]The yield was 95.1%.
[Bim][NO3]-NH3Preparing a solvent: weighing 5 parts of proton type ionic liquid [ Bim ]][NO3]Respectively placing in 10mL glass centrifuge tube, each 2g, plugging rubber plug with air inlet and outlet, introducing dry ammonia gas, and weighing to [ Bim][NO3]And NH3In a molar ratio of 1:0.5, 1:1, 1:1.5, 1:2, 1: 2.5. Measurement of the NH absorption by means of a viscometer (Lovis 2000M/ME, Olympa Co., Ltd.)3[ Bim ] of][NO3]The viscosity of (1) is 92%, 67%, 48%, 30%, 22% of the viscosity of the pure ionic liquid, and NH3The complex formulation of the (B) can obviously reduce the viscosity of the proton type ionic liquid.
Example 2 two-step Synthesis of proton-type Ionic liquids [ Bim][NTf2]：
This example illustrates the protic ionic liquid-NH-according to the invention3And (3) synthesis and preparation of a compound solvent.
(1) Taking 1-butylimidazole (0.1mol) and placing in a flask, takingPlacing a small excess amount of hydrochloric acid (0.103mol) in a constant-pressure funnel, dropwise adding the mixture into butylimidazole under the protection of nitrogen, carrying out magnetic stirring in ice bath, and continuously reacting at room temperature for 6 hours after dropwise adding; (2) after the reaction is finished, removing water from the mixture through rotary evaporation at the temperature of 65 ℃, and then transferring the mixture to a vacuum drying oven for 24 hours at the temperature of 60 ℃; (3) extracting and washing the crude product with ethyl acetate for 5 times, and then removing the organic solvent by rotary evaporation at 70 ℃ to obtain [ Bim][Cl]Yield 92.3%; (4) 0.05mol of [ Bim ] are respectively taken][Cl]And LiNTf2Putting (lithium bis (trifluoromethanesulfonyl) imide) into a flask, adding 50mL of deionized water, magnetically stirring at room temperature for 24h, protecting with dichloromethane after the reaction is finished, and extracting with a small amount of water for multiple times until the water phase adopts AgNO3Detecting the solution without generating precipitate; (5) then rotary evaporating at 70 deg.C for 50 deg.C to remove organic solvent and water, and vacuum drying (70 deg.C, 24 hr) and freeze drying at low temperature (-20 deg.C) to remove trace amount of water and organic solvent to obtain light yellow liquid product [ Bim][NTf2]The yield was 87.4%.
[Bim][NTf2]-NH3Preparing a solvent: weighing 5 parts of proton type ionic liquid [ Bim ]][NTf2]Respectively placing in 10mL glass centrifuge tube, each 2g, plugging rubber plug with air inlet and outlet, introducing dry ammonia gas, and weighing to [ Bim][NTf2]And NH3In a molar ratio of 1:0.5, 1:1, 1:1.5, 1:2, 1: 2.5. Measurement of the NH absorption by means of a viscometer (Lovis 2000M/ME, Olympa Co., Ltd.)3[ Bim ] of][NTf2]The viscosity of (1) is 94%, 70%, 51%, 31%, 24% of the viscosity of the pure ionic liquid, and NH3The complex formulation of the (B) can obviously reduce the viscosity of the proton type ionic liquid.
[ example 3 ]
This example serves to illustrate the electrolyte provided by the present invention.
At room temperature, 50 parts by weight of an organic solvent (consisting of dimethyl carbonate DMC, ethylene carbonate EC and diethyl carbonate DEC in a weight ratio of 1:1: 1), 20 parts by weight of lithium bistrifluoromethanesulfonylimide LiNTf230 parts by weight of [ Bim][NTf2]-NH3(1:1) mixing the compound solvent uniformly to prepare an electrolyte sample D1.
[ example 4 ]
This example serves to illustrate the electrolyte provided by the present invention.
At room temperature, 40 parts by weight of an organic solvent (consisting of dimethyl carbonate DMC, ethylene carbonate EC and diethyl carbonate DEC in a weight ratio of 1:1: 1), 20 parts by weight of lithium bistrifluoromethanesulfonylimide LiNTf240 parts by weight of [ Bim][NTf2]-NH3(1:1) mixing the compound solvent uniformly to prepare an electrolyte sample D2.
Comparative example 1
This comparative example was used to compare electrolytes with a protic ionic liquid alone as an additive.
At room temperature, 50 parts by weight of an organic solvent (consisting of dimethyl carbonate DMC, ethylene carbonate EC and diethyl carbonate DEC in a weight ratio of 1:1: 1), 20 parts by weight of lithium bistrifluoromethanesulfonylimide LiNTf230 parts by weight of [ Bim][NTf2]And mixing uniformly to prepare an electrolyte sample D3.
[ example 5 ] Rate Performance test
This example serves to illustrate the effect of the electrolyte on the rate performance of a lithium battery.
The 2032 coin cell is assembled by a method known by those skilled in the art, the positive active material is NCM523 (commercially available, and manufactured by manufacturers in the market), the negative active material is lithium plate (commercially available, and manufactured by manufacturers in the market is fenofibrate), the diaphragm material is PP (polypropylene), and the electrolyte is D1-D3. The lithium battery rate performance test result is as follows:
the test result shows that the ionic liquid is compared with the single proton type ionic liquid [ Bim][NTf2]As electrolyte additives, D1, D2 examples [ Bim][NTf2]-NH3The compound additive has obviously excellent rate performance. In the comparative example D3, the specific capacity retention rate of the proton type ionic liquid as the additive electrolyte can be significantly reduced to below 80% under the condition of high rate. D3 embodiesIn the prior art, the proton type ionic liquid has corrosion effect on a battery and an internal SEI film.
[ example 6 ]
This example serves to illustrate the effect of the electrolyte on the cycling performance of a lithium battery.
A 2032 coin cell was assembled as described in example 5, using methods known to those skilled in the art, with the positive electrode active material NCM523 (when liter), the negative electrode active material lithium plate (fibrate), the separator material PP (polypropylene), and the electrolyte solution D1-D3. The cycle performance test results of the lithium battery are shown in the attached drawings.
The test result shows that the ionic liquid is compared with the single proton type ionic liquid [ Bim][NTf2]As an electrolyte additive, [ Bim][NTf2]-NH3The compound additive has obviously excellent cycle performance. In the comparative example D3, the cycle performance of the electrolyte of the proton type ionic liquid as the additive is reduced rapidly, and after 80 cycles, the specific capacity is reduced to 80% of the initial specific capacity.
[ example 7 ]
This example is the same as example 2, except for the starting synthesis material. Synthesizing proton type ionic liquid by using 1-butyl pyrrolidine as raw material to obtain [ BPyr][NTf2]84% yield, followed by formulation [ BPyr][NTf2]： NH3The compound additive with the molar ratio of 1:1.
At room temperature, 40 parts by weight of an organic solvent (consisting of dimethyl carbonate DMC, ethylene carbonate EC and diethyl carbonate DEC in a weight ratio of 1:1: 1), 20 parts by weight of lithium bistrifluoromethanesulfonylimide LiNTf240 parts by weight of [ BPyr][NTf2]-NH3(1:1) mixing the compound solvent uniformly to prepare an electrolyte sample D4.
[ example 8 ]
This example is the same as example 2, except for the starting synthesis material. Synthesizing proton type ionic liquid by using 1-butyl piperidine as raw material to obtain [ BPiper ]][NTf2]Yield 86%, followed by formulation [ BPiper][NTf2]： NH3The compound additive with the molar ratio of 1:1.
At room temperature,40 parts by weight of organic solvent (consisting of dimethyl carbonate DMC, ethylene carbonate EC and diethyl carbonate DEC in a weight ratio of 1:1: 1) and 20 parts by weight of lithium bis (trifluoromethanesulfonylimide LiNTf)240 parts by weight of (BPiper)][NTf2]-NH3(1:1) mixing the compound solvent uniformly to prepare an electrolyte sample D5.
[ example 9 ]
This example is the same as example 2, except for the starting synthesis material. Synthesizing proton type ionic liquid by using 1-butylpyridine as raw material to obtain [ BPy][NTf2]Yield 70%, followed by formulation [ BPy%][NTf2]：NH3The compound additive with the molar ratio of 1:1.
At room temperature, 40 parts by weight of an organic solvent (consisting of dimethyl carbonate DMC, ethylene carbonate EC and diethyl carbonate DEC in a weight ratio of 1:1: 1), 20 parts by weight of lithium bistrifluoromethanesulfonylimide LiNTf240 parts by weight of [ BPy ]][NTf2]-NH3(1:1) mixing the compound solvent uniformly to prepare an electrolyte sample D6.
[ example 10 ]
This example is the same as example 2, except for the starting synthesis material. Synthesizing proton type ionic liquid by using 1, 4-dibutyl piperazine as raw material to obtain [1,4-2BPip][NTf2]86% yield, followed by formulation of [1,4-2BPip ]][NTf2]：NH3The compound additive with the molar ratio of 1:1.
At room temperature, 40 parts by weight of an organic solvent (consisting of dimethyl carbonate DMC, ethylene carbonate EC and diethyl carbonate DEC in a weight ratio of 1:1: 1), 20 parts by weight of lithium bistrifluoromethanesulfonylimide LiNTf240 parts by weight of [1,4-2BPip][NTf2]-NH3(1:1) mixing the compound solvent uniformly to prepare an electrolyte sample D7.
[ example 11 ]
This example serves to illustrate different types of protic ionic liquids/NH3The influence of the additive electrolyte on the rate capability of the lithium battery.
The 2032 coin cell is assembled by a method known by persons skilled in the art, the positive active material is NCM523 (when liter), the negative active material is lithium (fibrate), the diaphragm material is PP (polypropylene), and the electrolyte is D2 or D4-7. The lithium battery rate performance test results are as follows:
the test results show that the product is expressed as [ Bim][NTf2]-NH3、[BPyrr][NTf2]-NH3、[BPiper][NTf2]-NH3、 [BPy][NTf2]-NH3、[1,4-2BPip][NTf2]-NH3The rate capability of the lithium battery taking the compound solution as the additive can be kept above 80% under the condition of 5C, and the order of the rate capability maintenance is pyrrolidine proton type ionic liquid-NH3Solutions of>Piperidines>Piperazine-type imidazoles>Pyridines.
[ example 12 ]
This example is the same as example 7 except for the kind of lithium salt. Synthesizing proton type ionic liquid by using 1-butyl pyrrolidine as raw material to obtain [ BPyr][NTf2]84% yield, followed by formulation [ BPyr][NTf2]： NH3The compound additive with the molar ratio of 1:1.
At room temperature, 40 parts by weight of an organic solvent (consisting of dimethyl carbonate DMC, ethylene carbonate EC and diethyl carbonate DEC in a weight ratio of 1:1: 1), 20 parts by weight of lithium hexafluorophosphate LiPF 640 parts by weight of [ BPyr][NTf2]-NH3(1:1) mixing the compound solvent uniformly to prepare an electrolyte sample D8.
[ example 13 ]
This example serves to illustrate different types of lithium salts versus protic ionic liquid/NH3The influence of the rate capability of the lithium battery of the additive.
The 2032 coin cell is assembled by a method known by persons skilled in the art, the positive active material is NCM523 (when liter), the negative active material is lithium (fibrate), the diaphragm material is PP (polypropylene), and the electrolyte is D4 or D8. The lithium battery rate performance test results are as follows:
the foregoing is merely a preferred embodiment of the invention and is not intended to limit the scope of the invention, which is defined by the claims appended hereto, and any other technical entity or method that is encompassed by the claims as broadly defined herein, or equivalent variations thereof, is contemplated as being encompassed by the claims.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications can be made by those skilled in the art after reading the above disclosure, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (10)
1. An additive for an electrolyte for a lithium battery, characterized in that: the additive is obtained from the following components:
a protic ionic liquid component; and
NH3preparing components;
and said NH3The molar ratio of the ionic liquid to the proton type ionic liquid is (0.01-7): 1;
preferably, the proton type ionic liquid is selected from imidazole proton type ionic liquid, pyridine proton type ionic liquid, piperidine proton type ionic liquid, pyrrole proton type ionic liquid, piperazine proton type ionic liquid, quaternary amine proton type ionic liquid, pyrrolidine proton type ionic liquid or a combination thereof;
more preferably, the cation of the proton type ionic liquid is any one or combination of the following structures:
in the formulae (I) to (VII), R1And R2Each independently is H or alkyl with 1-12 carbon atoms, and at least one is-H; the R is3～R9H or C1-12 alkyl;
more preferably, the anion of the protic ionic liquid is selected from: cl-、Br-、I-、BF4 -、PF6 -、NO3 -、ClO4 -、HSO3 -、HSO4 -、H2PO4 -、CH3COO-、CH3(CH2)nCOO-、SCN-、SbF6 -、AsF6 -、CF3 -、CF3COO-、CH3SO4 -、C2H6SO4 -、C8H17SO4 -、C4F9SO3 -、CF3(CF2)nSO3 -、(CF3SO2)3C-、(C2F5SO2)2N-、(CF3SO2)2N-、CH3CH(OH)COO-One or more of dodecyl sulfonate, benzene sulfonate and p-toluene sulfonate, wherein n is independently selected from 0-12.
2. The method of claim 1An additive, wherein in the additive component, the protic ionic liquid component and NH3Hydrogen bonds are formed between the components.
3. The additive according to claim 1 or 2, wherein the protic ionic liquid is synthesized using a one-step process;
more preferably, in the one-step method, the proton-type ionic liquid is prepared by performing acid-base neutralization reaction on an acid corresponding to an anion and imidazole, pyridine, piperidine, pyrrole, piperazine, quaternary amine or pyrrolidine organic substances.
4. The additive according to claim 1 or 2, wherein the protic ionic liquid is synthesized using a two-step process;
preferably, when the anion of the protic ionic liquid is Cl-、Br-Or I-When the anion is not the same, the proton type ionic liquid is synthesized by adopting a two-step method; in the two-step method, the first step comprises the step of carrying out acid-base neutralization reaction on an acid corresponding to an anion and imidazole, pyridine, piperidine, pyrrole, piperazine, quaternary amine or pyrrolidine organic matters to obtain a salt; the second step comprises the step of carrying out anion exchange on the salt obtained in the first step to obtain the proton type ionic liquid;
preferably, when the anion of the protic ionic liquid is Cl-、Br-Or I-Then the proton type ionic liquid obtained by the two-step method is subjected to anion exchange with corresponding salt to obtain Cl as an anion-、Br-Or I-The proton type ionic liquid of (1).
5. Use of an additive according to any one of claims 1-4 in an electrolyte for a lithium battery.
6. An electrolyte for a lithium battery comprising the additive of any one of claims 1 to 4, wherein the electrolyte comprises an organic solvent, a lithium salt, and an additive;
preferably, the electrolyte comprises the following components:
10-80 parts by weight of an organic solvent,
5 to 70 parts by weight of a lithium salt, and
1-80 parts of additive.
7. The electrolyte for a lithium battery according to claim 6, wherein the organic solvent is one or more selected from a chain acid ester and a cyclic acid ester;
preferably, the chain acid ester is selected from a fluorine-containing chain organic ester, a sulfur-containing chain organic ester, an unsaturated bond-containing chain organic ester, or a combination thereof; more preferably, the chain acid ester is selected from dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propyl methyl carbonate, dipropyl carbonate or a combination thereof;
preferably, the cyclic acid ester is selected from a fluorine-containing cyclic organic ester, a sulfur-containing cyclic organic ester, or an unsaturated bond-containing cyclic organic ester, or a combination thereof; more preferably, the cyclic acid ester is selected from ethylene carbonate, propylene carbonate, vinylene carbonate, gamma-butyrolactone, sultone, or combinations thereof;
preferably, the lithium salt is selected from lithium tetrafluoroborate, lithium hexafluorophosphate, lithium perchlorate, lithium hexafluoroarsenate, lithium halides, lithium chloroaluminate, lithium bistrifluoromethanesulfonylimide, lithium bisfluorosulfonylimide, lithium dioxalate borate or combinations thereof.
8. A method for preparing the electrolyte for a lithium battery as claimed in claim 6 or 7, characterized by comprising the steps of:
providing an organic solvent, a lithium salt, and an additive, wherein the additive is derived from components comprising: proton type ionic liquid component and NH3Preparing components; and said NH3The molar ratio of the ionic liquid to the proton type ionic liquid is (0.01-7): 1;
mixing the components to obtain the electrolyte for the lithium battery;
preferably, the proton type ionic liquid is synthesized by adopting a one-step method or a two-step method.
9. Use of an electrolyte for a lithium battery according to claim 6 or 7 in a lithium battery, wherein the electrolyte contains an organic solvent, a lithium salt and an additive, wherein the additive is obtained from a composition comprising:
a protic ionic liquid component; and
NH3preparing components;
and said NH3The molar ratio of the ionic liquid to the proton type ionic liquid is (0.01-7): 1.
10. a lithium battery comprising a core and an electrolyte, the core and the electrolyte being sealed in a battery case, characterized in that the electrolyte is the electrolyte of claim 6 or 7.
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