CN117013083A - Lithium ion battery electrolyte and battery thereof - Google Patents

Lithium ion battery electrolyte and battery thereof Download PDF

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Publication number
CN117013083A
CN117013083A CN202210470455.4A CN202210470455A CN117013083A CN 117013083 A CN117013083 A CN 117013083A CN 202210470455 A CN202210470455 A CN 202210470455A CN 117013083 A CN117013083 A CN 117013083A
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lithium
electrolyte
ion battery
carbonate
positive electrode
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王群峰
何亚宁
施开赢
陶亮
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Sinochem International Corp
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Sinochem International Corp
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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
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)

Abstract

The invention discloses an electrolyte of a lithium ion battery and the battery thereof, wherein the electrolyte comprises an organic solvent and lithium salt, wherein the organic solvent comprises a chain ether compound and a carbonate solvent shown in the following formula I, wherein n and R in the formula I 1 、R 2 、R 3 As described herein. The electrolyte can solve the problem of poor wettability of the high-compaction-density electrode plate and the electrolyte, so that the low-temperature performance, the normal-temperature and high-temperature cycle performance of the lithium ion battery are improved, and the service life of the lithium ion battery is effectively prolonged.

Description

Lithium ion battery electrolyte and battery thereof
Technical Field
The invention belongs to the field of lithium ion batteries, and relates to a high-compaction-density lithium iron phosphate battery electrolyte and a battery containing the electrolyte.
Background
LiFePO of olivine structure 4 Has a discharge ratio ofThe positive electrode material has the advantages of high capacity, stable discharge platform, stable structure, excellent cycle performance, rich raw materials and the like, and is considered as an ideal positive electrode material of the power type lithium ion battery. However, the low-temperature performance of lithium iron phosphate lithium ion batteries is poor, and the main reason is that lithium iron phosphate belongs to a Pnma space group, P occupies a tetrahedral position, transition metal M occupies an octahedral position, and Li atoms form a migration channel along the one-dimensional direction of an axis, and the one-dimensional ion channel causes lithium ions to be extracted or intercalated only orderly in a single mode, so that the diffusion capability of lithium ions in the material is seriously affected. Particularly, the diffusion of lithium ions in the body is further hindered at low temperature, so that the impedance is increased, the polarization is more serious, and the low-temperature performance is poor.
In addition, the energy density of lithium iron phosphate batteries is low. To increase the energy density, on the one hand, the gram capacity of the anode and cathode materials is increased, and on the other hand, the compacted density of the anode and cathode films is increased. In the common lithium iron phosphate battery core, the compaction density of the positive plate is 2.1-2.3g/cm 3 The positive electrode compaction density of the lithium iron phosphate battery core is improved to 2.35-2.8g/cm by various technologies in the range of battery enterprises 3 Is a level of (c). However, the improvement of compaction density causes great difficulty on the liquid absorption capacity and the liquid absorption time of the pole piece and the diaphragm, the liquid absorption capacity of the battery core is too small, the wettability of the electrode piece and the electrolyte is poor, the low-temperature performance is poor, and adverse phenomena such as water jump and the like occur in later-stage circulation of the battery. Therefore, improvement of the low-temperature performance of the lithium iron phosphate battery under the high-compaction-density electrode slice system from the viewpoint of electrolyte is urgently needed.
However, under low temperature conditions, part of the solvent in the electrolyte is precipitated, resulting in difficulty in ion migration, low conductivity, and low temperature resulting in lithium ion diffusion and a reduction in charge transfer rate. Therefore, the search for an electrolyte with good matching with high-compaction lithium iron phosphate is very significant for improving the performance of lithium iron phosphate batteries and meeting the future further development of high-energy-density batteries.
Disclosure of Invention
In order to solve the problem of poor low-temperature performance of a high-compaction-density lithium iron phosphate lithium ion battery in the prior art, the invention provides the lithium iron phosphate battery electrolyte which can solve the problem of poor wettability of a high-compaction-density electrode plate and the electrolyte, so that the low-temperature performance, normal temperature and high-temperature cycle performance of the lithium iron phosphate battery are improved, and the service life of the lithium iron phosphate battery is effectively prolonged.
Specifically, the invention provides an electrolyte of a lithium ion battery, which comprises an organic solvent and lithium salt, wherein the organic solvent comprises a chain ether compound shown in a formula I and a carbonate solvent:
R 1 -O-(R 2 -O) n -R 3
I
in the formula I, n is an integer more than or equal to 1;
each R is 2 Each independently selected from linear or branched C 1 -C 6 Alkylene and straight-chain or branched C 2 -C 6 Alkenylene radicals, each R 2 Optionally one or more H on carbon atoms of (c) may be substituted with a group selected from: alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkyloxy, heterocyclyl, heterocyclyloxy, aryl, aryloxy, heteroaryl, nitro, ester, halogen, and aldehyde groups;
R 1 and R is 3 Each independently selected from hydrogen atoms, C 1 -C 6 Alkyl, C 3 -C 6 Cycloalkyl, ternary to six membered heterocyclyl, C 2 -C 6 Alkenyl and C 2 -C 6 One or more of the alkynyl groups, the R 1 And R is 3 Optionally one or more H on carbon atoms of (c) may be substituted with a group selected from: alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkyloxy, heterocyclyl, heterocyclyloxy, aryl, aryloxy, heteroaryl, nitro, ester, halogen, and aldehyde groups.
In one or more embodiments, in formula I, n is an integer between 1 and 6, preferably 1.
In one or more embodiments, each R 2 Each independently selected from linear or branched C 1 -C 4 Alkylene and straight-chain or branched C 2 -C 4 Alkenylene, preferably selected from linear or branched C 2 -C 4 Alkylene groupA base.
In one or more embodiments, R 1 And R is 3 Each independently selected from linear or branched C 1 -C 6 Alkyl groups, preferably selected from methyl and ethyl.
In one or more embodiments, the chain ether compound is selected from one or more of ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol diethyl ether, 1, 4-butanediol dimethyl ether, 1, 4-butanediol diethyl ether, and 1, 4-butanediol methyl ethyl ether.
In one or more embodiments, the chain ether compound accounts for not less than 3% of the organic solvent by mass.
In one or more embodiments, the chain ether compound comprises < 10% by mass of the organic solvent.
In one or more embodiments, the carbonate-based solvent includes at least one cyclic carbonate including one or more selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate, and gamma-butyrolactone, and at least one chain carbonate including one or more selected from the group consisting of dimethyl carbonate, diethyl carbonate, and ethylmethyl carbonate.
In one or more embodiments, the concentration of the lithium salt in the electrolyte is 0.5 to 2mol/L.
In one or more embodiments, the lithium salt is selected from one or more of lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide, lithium bis (oxalato) borate, lithium difluorooxalato borate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, lithium fluoride, and lithium trifluoromethanesulfonate.
The invention also provides a lithium ion battery, which comprises a positive electrode plate, a negative electrode plate and the electrolyte of any embodiment.
In one or more embodiments, the positive electrode active material contained in the positive electrode sheet includes lithium iron phosphate.
In one or more embodiments, the positive electrode sheet includes a positive electrode material layer, an electrode layerThe positive electrode material layer has a compacted density of D g/cm 3 The chain ether compound accounts for W% of the organic solvent, and the following relation is satisfied by D and W: D/W is more than or equal to 0.3 and less than or equal to 0.6.
In one or more embodiments, the positive electrode active material contained in the positive electrode sheet is lithium iron phosphate containing Mg, the weight content of the Mg is X ppm, X is more than or equal to 350 and less than or equal to 20000 based on the total weight of the positive electrode active material, the chain ether compound accounts for W% of the organic solvent, and the following relationship is satisfied between X and W: X/W is more than or equal to 30 and less than or equal to 6000.
In one or more embodiments, the negative electrode active material contained in the negative electrode sheet is selected from lithium metal, graphite, mesophase carbon spheres, hard carbon, soft carbon, silicon-carbon composite, li-Sn alloy, li-Sn-O alloy, spinel structured lithiated TiO 2 -Li 4 Ti 5 O 12 And one or more of Li-Al alloys.
In one or more embodiments, the lithium ion battery is a cylindrical lithium ion battery, a soft-pack lithium ion battery, or an aluminum-shell lithium ion battery.
Drawings
Fig. 1 is a graph showing comparison of direct current internal resistance (DCR) test results at-20 ℃ for the lithium ion batteries of comparative example 1 and example 1.
Fig. 2 is a comparative graph showing the results of the low-temperature discharge capacity retention test at-20 c for the lithium ion batteries of comparative example 1 and example 1.
Fig. 3 is a comparative graph showing the results of the test of the retention rate of the discharge capacity at-20C with a large current of 2C for the lithium ion batteries of comparative example 1 and example 1.
Fig. 4 is a comparative graph showing the results of the high-current charge capacity retention test at-20C for the lithium ion batteries of comparative example 1 and example 1.
Fig. 5 is a graph comparing the results of the 45 ℃ cycle capacity retention test of the lithium ion batteries of comparative example 1 and example 1.
Detailed Description
So that those skilled in the art can appreciate the features and effects of the present invention, a general description and definition of the terms and expressions set forth in the specification and claims follows. Unless otherwise defined, 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, and in the event of a conflict, the present specification shall control.
The theory or mechanism described and disclosed herein, whether right or wrong, is not meant to limit the scope of the invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
Herein, "comprising," "including," "containing," and similar terms are intended to cover the meaning of "consisting essentially of … …" and "consisting of … …," e.g., "a consisting essentially of B and C" and "a consisting of B and C" should be considered to have been disclosed herein when "a comprises B and C" is disclosed herein.
In this document, all features such as values, amounts, and concentrations that are defined as ranges of values or percentages are for brevity and convenience only. Accordingly, the description of a numerical range or percentage range should be considered to cover and specifically disclose all possible sub-ranges and individual values (including integers and fractions) within the range.
Herein, unless otherwise specified, percentages refer to mass percentages, and proportions refer to mass ratios.
Herein, when embodiments or examples are described, it should be understood that they are not intended to limit the invention to these embodiments or examples. On the contrary, all alternatives, modifications, and equivalents of the methods and materials described herein are intended to be included within the scope of the invention as defined by the appended claims.
In this context, not all possible combinations of the individual technical features in the individual embodiments or examples are described in order to simplify the description. Accordingly, as long as there is no contradiction between the combinations of these technical features, any combination of the technical features in the respective embodiments or examples is possible, and all possible combinations should be considered as being within the scope of the present specification.
The invention discovers that adding chain ether compounds into the electrolyte of lithium ion batteries, in particular lithium ion batteries with lithium iron phosphate as the positive electrode active material (herein called lithium iron phosphate batteries for short), is beneficial to improving the electrolyte wettability of the positive electrode material under high compaction density, and improves the cycle performance, low-temperature performance and high-rate charge and discharge performance of the lithium ion batteries. By introducing a proper amount of Mg element into lithium iron phosphate on the basis of adding a chain ether compound into the electrolyte, the high-temperature stability can be further improved while the excellent low-temperature performance is ensured.
Chain ether compound
The invention discovers that the chain ether compound has lower viscosity and melting point, can reduce the surface tension of the electrolyte after being added into the electrolyte, improve the wettability of the electrolyte to the high-compaction positive and negative plates and the diaphragm, improve the liquid absorption capacity of the battery core, reduce the activation time of the battery core, improve the production efficiency and save the production cost; the chain ether compound is mixed with other common carbonate solvents to form an electrolyte solvent with extremely low eutectic point, so that the electrolyte of the lithium ion battery can still keep a liquid phase at low temperature, and the utilization efficiency of activated substances is improved. On the other hand, the coordination capacity of the chain ether compound is weaker, so that the coordination structure of the original carbonate solvent and lithium ions is not changed after the addition, the characteristic of high stability of the carbonate electrolyte is maintained, but the viscosity of the electrolyte is effectively reduced, the dissociation degree of the lithium ions is increased, and the conductivity of the electrolyte is greatly improved.
The chain ether compound suitable for the invention has a structure shown in the following formula I:
R 1 -O-(R 2 -O) n -R 3
I
in the formula I, n is an integer more than or equal to 1;
each R is 2 Each independently selected from linear or branched C 1 -C 6 Alkylene and straight-chain or branched C 2 -C 6 Alkenylene radicals, each R 2 Optionally one or more H on carbon atoms of (c) may be substituted with a group selected from: alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkyloxy, heterocyclyl, heterocycleAcyloxy, aryl, aryloxy, heteroaryl, nitro, ester, halogen and aldehyde groups;
R 1 and R is 3 Each independently selected from hydrogen atoms, C 1 -C 6 Alkyl, C 3 -C 6 Cycloalkyl, ternary to six membered heterocyclyl, C 2 -C 6 Alkenyl and C 2 -C 6 One or more of the alkynyl groups, the R 1 And R is 3 Optionally one or more H on carbon atoms of (c) may be substituted with a group selected from: alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkyloxy, heterocyclyl, heterocyclyloxy, aryl, aryloxy, heteroaryl, nitro, ester, halogen, and aldehyde groups.
In the present invention, halogen includes fluorine, chlorine, bromine, iodine. In the present invention, alkenyl and alkynyl groups as substituents preferably have 2 to 6, for example 2 to 3 carbon atoms. The alkoxy groups and ester groups as substituents preferably have 1 to 6, for example 1 to 3, carbon atoms. Cycloalkyl and cycloalkyloxy groups as substituents preferably have 3 to 6 carbon atoms. The heterocyclic group and the heterocyclyloxy group as the substituent are preferably 3-10 membered ring systems, for example, 5-6 membered ring systems. Aryl, aryloxy and heteroaryl groups as substituents are preferably 5-10 membered ring systems, for example 5-6 membered ring systems.
In some embodiments, R 1 、R 2 And/or R 3 The above substituents are absent.
Preferably, in formula I, n is 1, 2, 3, 4, 5 or 6, preferably 1.
Preferably, in formula I, each R 2 Each independently selected from linear or branched C 1 -C 4 Alkylene and straight-chain or branched C 2 -C 4 Alkenylene, preferably selected from linear or branched C 2 -C 4 Alkylene groups such as ethylene, 1, 3-propylene, 1, 4-butylene.
Preferably, R 1 And R is 3 Each independently selected from linear or branched C 1 -C 6 Alkyl, preferably selected from linear or branched C 1 -C 4 Alkyl groups such as methyl and ethyl.
In some embodiments, the chain ether compound is selected from one or more of ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol diethyl ether, 1, 4-butanediol dimethyl ether, 1, 4-butanediol diethyl ether, and 1, 4-butanediol methyl ethyl ether.
In the present invention, one or more kinds of chain ether compounds may be added to the electrolyte. In the electrolyte, the chain ether compound preferably accounts for less than 10% of the mass of the organic solvent. The invention discovers that the HOMO value of the chain ether compound is higher, and the chain ether compound is easily oxidized at the positive electrode, so that the stability of the interface of the positive electrode is poor, and the structural fracture is caused, so that the addition amount is controlled to be less than 10%. In order to ensure the impregnating effect, the chain ether compound preferably occupies not less than 3% by mass of the organic solvent, for example, 4%, 5%, 5.5%, 6%, 7%, 8%, 9%.
Lithium ion battery electrolyte
The lithium ion battery electrolyte (herein abbreviated as electrolyte) includes an organic solvent and a lithium salt. The organic solvent commonly used for the electrolyte is a carbonate-based solvent. The electrolyte is characterized in that the organic solvent also comprises the chain ether compound. Therefore, the invention also provides application of the chain ether compound in preparing lithium ion battery electrolyte. In some embodiments, the organic solvent in the electrolyte of the present invention comprises or consists of a carbonate-based solvent and a chain ether-based compound.
The carbonate-based solvent suitable for the electrolyte of the present invention may be a carbonate-based solvent commonly used in the art for electrolytes, including, but not limited to, one or more, preferably two or more, selected from the group consisting of Ethylene Carbonate (EC), propylene Carbonate (PC), butylene carbonate, γ -butyrolactone, dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethylmethyl carbonate (EMC). Preferably, the carbonate-based solvent comprises at least one cyclic carbonate and at least one chain carbonate. Examples of the cyclic carbonates include ethylene carbonate, propylene carbonate, butylene carbonate and γ -butyrolactone. Examples of the chain carbonates include dimethyl carbonate, diethyl carbonate and methylethyl carbonate. The mass ratio of cyclic carbonate to chain carbonate may be 1:4 to 2:3, for example 2:7, 1:3, 3:7, 30:67, 30:65, 30:64.5, 30:64, 30:63, 30:62, 30:61, 1:2. In some embodiments, the cyclic carbonate is ethylene carbonate and the chain carbonate is methyl ethyl carbonate.
In the electrolyte of the present invention, the mass of the carbonate-based solvent is preferably 90% to 97%, for example 91%, 92%, 93%, 94%, 95%, 96% of the total mass of the organic solvent.
The electrolyte of the present invention may optionally contain an organic solvent other than the carbonate-based solvent and the cyclic ether-based solvent, which may be used for the electrolyte, including, but not limited to, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, propyl propionate, butyl propionate, etc.
The lithium salt in the electrolyte of the present invention may be a lithium salt commonly used in the art, including but not limited to lithium hexafluorophosphate (LiPF) 6 ) Lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium bis (fluorosulfonyl) imide (LiLiFSI), lithium bis (oxalato) borate (LiBOB), lithium difluorooxalato borate (LiODFB), lithium tetrafluoroborate (LiBF) 4 ) Lithium hexafluoroarsenate (LiAsF) 6 ) Lithium perchlorate (LiClO) 4 ) Lithium fluoride (LiF), lithium triflate (LiCF) 3 SO 3 ) Etc. In some embodiments, the lithium salt is LiPF 6 . The concentration of the lithium salt in the electrolyte may be 0.5 to 2mol/L, for example 0.8mol/L, 0.9mol/L, 1mol/L, 1.1mol/L, 1.2mol/L, 1.5mol/L.
The electrolyte of the present invention may optionally contain other known additives useful in lithium ion battery electrolytes, such as desolvation agents, co-solvents, film-forming additives, and the like. The mass fraction of the additive in the electrolyte may be 0.1% to 10%, for example 1% to 5%, 2%, 3%, 4%.
The electrolyte of the present invention may be prepared by the following method: firstly, uniformly mixing a carbonate solvent and lithium salt to obtain a carbonate solution of the lithium salt, and then adding a chain ether compound into the carbonate solution of the lithium salt to uniformly mix; or mixing carbonate solvent and chain ether compound, adding lithium salt, and mixing.
Lithium ion battery
The lithium ion battery comprises a positive pole piece, a negative pole piece, a diaphragm and an electrode liquid. The electrolyte is suitable for various lithium ion batteries, such as lithium iron phosphate batteries, and particularly high-compaction-density lithium iron phosphate batteries. In the invention, the lithium iron phosphate battery refers to a lithium ion battery with a positive electrode active material of lithium iron phosphate. The invention provides a lithium ion battery with an electrolyte comprising a cyclic ether solvent or the electrolyte as described in any one of the embodiments herein.
And laminating (such as Z-shaped lamination or winding lamination) the positive pole piece, the negative pole piece and the isolating film according to design requirements to obtain the battery core of the lithium ion battery.
The positive electrode plate comprises a positive electrode current collector and a positive electrode material layer formed on the surface of the positive electrode current collector. The positive electrode material layer includes a positive electrode active material, a conductive agent, and a binder. The positive electrode material layer is prepared by coating positive electrode slurry containing positive electrode active material, conductive agent, binder and solvent on a positive electrode current collector, and then rolling, die cutting and baking. The solvent of the positive electrode slurry may be N-methylpyrrolidone (NMP). The positive electrode current collector may be copper foil, aluminum foil, titanium foil, nickel foil, iron foil, zinc foil, or the like. The positive electrode active material may be selected from lithium iron phosphate, a binary positive electrode material, a ternary positive electrode material, a quaternary positive electrode material, and the like. Preferably, the positive electrode active material is lithium iron phosphate. The conductive agent of the positive electrode may be one or more selected from conductive carbon black (SP), carbon Fiber (CF), acetylene black, conductive graphite, graphene, carbon nanotube, and carbon microsphere. The binder of the positive electrode may be one or more selected from polyvinylidene fluoride (PVDF), polytetrafluoroethylene, polyvinyl alcohol, polyolefin, styrene-butadiene rubber, fluorinated rubber, polyurethane, and sodium alginate. In some embodiments, the conductive agent in the positive electrode material layer is SP and the binder is PVDF. The content ratio of each component in the positive electrode material layer may be conventional, for example, the mass fraction of the positive electrode active material may be 90% -98%, for example 92%, 94%, 96%, 96.7%, 97%, the mass fraction of the conductive agent may be 1% -5%, for example 1.2%, 1.5%, 2%, 3%, 3.5%, 4%, and the mass fraction of the binder may be 1% -5%, for example 1.5%, 1.8%, 2%, 2.5%, 3%, 4%.
The positive electrode material layer of the positive electrode plate in the lithium ion battery preferably has higher compaction density which is preferably more than or equal to 2.4g/cm 3 Preferably 2.4-2.75g/cm 3 More preferably 2.45-2.7g/cm 3 For example 2.5g/cm 3 、2.55g/cm 3 、2.6g/cm 3 、2.65g/cm 3 . It is generally considered that the compaction density of the positive electrode material layer on the positive electrode sheet is not less than 2.45g/cm 3 (e.g., 2.45-2.65 g/cm) 3 、2.55g/cm 3 ) Is a high compaction density. For lithium ion battery density cells, particularly lithium iron phosphate cells, the present invention has found that the compacted density D (g/cm 3 ) And the weight percentage W (%) of the chain ether compound in the electrolyte to occupy the organic solvent is controlled to be more than or equal to 0.3 and less than or equal to 0.6, such as 0.31, 0.33, 0.35, 0.4, 0.45, 0.47, 0.5 and 0.55, the dynamic performance (-20 ℃ direct current impedance and discharge capacity retention rate) of the high-compaction density battery can be effectively improved, and the high-temperature cycle performance can not be deteriorated.
In some preferred embodiments, the positive electrode active material is lithium iron phosphate containing Mg element. The content of Mg element in the lithium iron phosphate containing Mg element is preferably 350 to 20000ppm, for example 400ppm, 500ppm, 700ppm, 1000ppm, 2000ppm, 2500ppm, 4000ppm, 7000ppm, 10000ppm. Preferably, the invention controls the content X (ppm) of Mg element in lithium iron phosphate and the mass percent W (%) of chain ether compound in electrolysis to be less than or equal to 30 and less than or equal to 6000, such as 50, 100, 250, 500, 1000, 2000 and 3000, so that the lithium ion battery has higher high-temperature cycle capacity retention rate and low-temperature discharge capacity retention rate.
The negative pole piece comprises a negative pole current collector and a negative pole material layer arranged on the surface of the negative pole current collector. The negative electrode current collector may be copper foil. The anode material layer includes an anode active material, a conductive agent, and a binder. The negative electrode material layer is prepared by coating a negative electrode slurry containing a negative electrode active material, a conductive agent, a binder and a solvent on a positive electrode current collector, and then rolling, die-cutting and baking. The solvent of the anode slurry may be water. The negative electrode active material may be selected from graphite (including natural graphite, artificial graphite), lithium metal (includingStructured lithium metal), mesophase carbon spheres, hard carbon, soft carbon, silicon-carbon composites, li-Sn alloys, li-Sn-O alloys, spinel structured lithiated TiO 2 -Li 4 Ti 5 O 12 And one or more of Li-Al alloys. The negative electrode conductive agent may be one or more selected from conductive carbon black (SP), acetylene black, carbon nanotubes, carbon nanowires, carbon microspheres, carbon fibers, and graphene. The negative electrode binder may be one or more selected from polyvinylidene fluoride, polytetrafluoroethylene, acrylonitrile copolymer, polybutyl acrylate, polyacrylonitrile, and Styrene Butadiene Rubber (SBR). The anode material layer and the anode slurry may further contain a thickener such as sodium carboxymethyl cellulose (CMC). In some embodiments, the negative electrode active material in the negative electrode material layer is graphite, the conductive agent is conductive carbon black, the binder is styrene-butadiene rubber, and the thickener is sodium carboxymethyl cellulose. The mass ratio of each component in the anode material layer may be conventional, for example, the mass fraction of the anode active material may be 90% to 98%, for example 93%, 95%, 95.7%, 96%, 97%, the mass fraction of the conductive agent may be 0.5% to 5%, for example 1%, 1.5%, 2%, the mass fraction of the binder may be 0.5% to 5%, for example 1%, 1.5%, 2%, 3%, and the mass fraction of the thickener may be 0 to 5%, for example 1%, 1.5%, 1.8%, 2%, 3%.
The membrane may be a polymer membrane, a ceramic membrane or a polymer/ceramic composite membrane. The polymer separator includes a single layer polymer separator and a multi-layer polymer separator. The single layer polymer separator includes a Polyethylene (PE) separator and a polypropylene (PP) separator.
And after the battery cell is obtained, packaging the battery cell in a shell, and drying, injecting liquid (injecting electrolyte), packaging, standing, forming and shaping to obtain the lithium ion battery. The form of the lithium ion battery of the present invention is not particularly limited, and may be a cylindrical lithium ion battery, a soft pack lithium ion battery, or an aluminum case lithium ion battery.
The invention has the following beneficial effects: the invention provides a non-aqueous electrolyte of a lithium ion battery, which is used by optimizing electrolyte components, namely introducing a weak-polarity chain ether compound to be matched with a carbonate solvent system, and preferably controlling the dosage of the chain ether compound and the compaction density of a positive electrode material layer, so that electrolyte infiltration of a positive electrode active material, particularly lithium iron phosphate, under high compaction density is improved, and the problems that the electrolyte absorption capacity of each diaphragm of a pole piece is insufficient, the activation time is long and the polarization is large due to overlarge compaction density of a positive electrode plate of the high-compaction lithium ion battery, particularly the lithium iron phosphate battery, are effectively solved, thereby influencing the cycle performance, the low-temperature discharge performance and the high-rate charge-discharge performance of the battery.
The invention will be illustrated by way of specific examples. It should be understood that these examples are illustrative only and are not intended to limit the scope of the invention. The methods, reagents and materials used in the examples are those conventional in the art unless otherwise indicated. The starting compounds in the examples are all commercially available. The lithium iron phosphate doped with Mg element in the examples was purchased from Qinghai taifeng advanced lithium energy technologies limited.
In the invention, the compaction density D of the positive pole piece is calculated by the formula: d=m/v calculated. Wherein m is the mass of the positive electrode material layer, and the unit is: g; v is the volume of the positive electrode material layer, unit: cm 3 Wherein the volume v is the product of the area of the positive electrode material layer and the thickness of the positive electrode material layer.
Examples 1 to 29 and comparative examples 1 to 2
The lithium ion batteries in examples and comparative examples were prepared as follows:
1) Electrolyte preparation
In an argon atmosphere glove box with a water content of < 10ppm, ethylene Carbonate (EC), ethylmethyl carbonate (EMC) and diluent were mixed uniformly according to the mass ratio in tables 1 and 2, and LiPF was added 6 Stirring uniformly to form electrolyte, wherein LiPF 6 The concentration of (C) was 1.1mol/L.
2) Preparation of positive plate
The positive electrode active material lithium iron phosphate or lithium iron phosphate doped with Mg (wherein, the lithium iron phosphate doped with Mg is used in examples 1-28 and comparative example 1, the doping amount of Mg is 2500ppm in examples 1-18 and comparative example 1, the doping amount of Mg is shown in table 2 in examples 19-28, the lithium iron phosphate doped with no Mg is used in examples 29 and comparative example 2), a conductive agent SP, a binder polyvinylidene fluoride (PVDF) and a solvent of N-methyl pyrrolidone (NMP) are fully stirred and mixed according to the weight ratio of 96.7:1.5:1.8 to form uniform positive electrode slurry; the slurry is coated on an Al foil of a positive electrode current collector, dried and cold-pressed to obtain positive electrode plates, and the compaction density of a positive electrode material layer on each positive electrode plate is shown in tables 1 and 2.
3) Preparation of negative plate
Fully stirring and mixing negative electrode active material graphite, a conductive agent SP, a binder Styrene Butadiene Rubber (SBR) and a thickener sodium carboxymethylcellulose (CMC) in a proper amount of deionized water solvent according to a weight ratio of 95.7:1:1.5:1.8 to form uniform negative electrode slurry; and (3) coating the slurry on a negative current collector Cu foil, and drying and cold pressing to obtain a negative plate.
4) Diaphragm preparation
The diaphragm is made of polyethylene (PE diaphragm).
5) Preparation of lithium ion batteries
And sequentially stacking the positive plate, the diaphragm and the negative plate, enabling the diaphragm to be positioned between the positive plate and the negative plate to play a role of isolation, winding, placing the wound positive plate and the negative plate in an outer packaging foil, injecting the prepared electrolyte into a dried battery, and performing procedures such as vacuum packaging, standing, formation, shaping and the like to prepare the lithium ion battery.
Test case
The following performance tests were performed on the lithium ion batteries of examples and comparative examples, and the test results are shown in tables 1, 2 and fig. 1 to 5.
1) High temperature cycle test
Placing the lithium ion battery in a 45 ℃ incubator, and standing for 30 minutes to keep the lithium ion battery constant; discharging to 2V at constant current of 1C, and standing for 30 minutes; charging to 3.65V with 1C constant current, and charging to 0.05C constant voltage; standing for 30 minutes; then discharging to 2.0V by using 1C, and recording as the 1 st cycle discharge capacity by taking the capacity as a reference; this step was cycled 500 times, the discharge capacity at 500 th cycle was recorded, and the capacity retention rate was calculated.
Capacity retention after 500 cycles (%) =discharge capacity at 500 th cycle/discharge capacity at 1 st cycle×100%
2) Direct current impedance (DCR) test of lithium ion battery at-20 DEG C
Standing the lithium ion battery in a high-low temperature box at the temperature of minus 20 ℃ for 30 minutes to keep the lithium ion battery at a constant temperature; discharging to 2V at constant current of 1C, and standing for 30 minutes; then discharging to 3.65V with 1C constant current, charging to 0.05C constant voltage, standing for 30min, and obtaining the actual capacity. Discharging for 15min with constant current of 2C (calculated by the actual capacity obtained in one step above the capacity), and recording the voltage at the moment as V1; and then discharging for 10s by using a 2C constant current (the capacity is calculated by using the nominal capacity of the lithium ion battery), recording the voltage at the moment as V2, and calculating the corresponding direct current impedance of the lithium ion battery in the state of charge (SOC state) of 50 percent of the battery.
50% SOC DC impedance= (V1-V2)/2C
3) 2C constant current charging rate test
Standing the lithium ion battery in a high-low temperature box at the temperature of minus 20 ℃ for 30 minutes to keep the lithium ion battery at a constant temperature; then discharging to 2V with constant current of 1C, and standing for 30 minutes; then charging to 3.65V at constant current of 0.33C, standing for 30min, and recording the charging capacity Q1; discharge capacity Q2 was recorded at a constant current discharge of 2C to a cutoff voltage of 3.65V. And calculating the capacity retention rate of the low-temperature 2C constant-current charging rate.
Low temperature 2C charge capacity retention = Q2/Q1 x 100%.
4) 2C constant-current discharge rate test
Standing the lithium ion battery in a high-low temperature box at the temperature of minus 20 ℃ for 30 minutes to keep the lithium ion battery at a constant temperature; discharging to 2V at constant current of 1C, and standing for 30 minutes; then charging to 3.65V with a constant current of 1C, charging to a constant voltage of 0.05C, and standing for 30 minutes; discharge capacity Q1 was recorded at 0.33C constant current discharge to 2V. Then charging to 3.65V with a constant current of 1C, charging to a constant voltage of 0.05C, and standing for 30 minutes; discharge capacity Q2 was recorded at a constant current discharge of 2C to 2V. And calculating the capacity retention rate of the low-temperature 2C constant-current discharge rate.
Low temperature 2C discharge capacity retention = Q2/Q1 x 100%.
5) -20 ℃ low temperature discharge test
The lithium ion battery was tested as follows: 1) Standing for 1h in a high-low temperature box at 25 ℃; 2) Constant-current charging to 4.45V at 0.7C, constant-voltage charging to 0.05C, and standing for 10min; 3) Constant-current discharging to 3.0V at 0.2C, standing for 5min, and recording discharge capacity C1; 4) Standing at-20deg.C for 30min, constant-current charging at 0.7deg.C to 4.45V, constant-voltage charging at 0.05C, and standing for 10min; 5) Constant-current discharging to 3.0V at 0.2C, standing for 5min, and recording discharge capacity C2; 6) The low-temperature discharge capacity retention rate was calculated.
Low temperature discharge capacity retention = C2/c1×100%.
Table 1: lithium ion battery preparation parameters and test results of examples 1-18 and comparative example 1
Note that: in Table 1, D is the compacted density (unit: g/cm) of the positive electrode material layer on the positive electrode sheet 3 ) W is the mass fraction of diluent in the organic solvent (unit: % of the total weight of the composition.
As is clear from comparative example 1 of Table 1, the DCR at-20℃and the low-temperature discharge and 2C high-rate charge-discharge properties of the battery were poor without adding the weakly polar alkyl chain ether solvent.
As is clear from comparative examples 1 and 1, the introduction of the weakly polar alkyl chain ether solvent can significantly improve the DCR at-20 ℃ and the low-temperature discharge and 2C high-rate charge-discharge performance of the battery, and slightly improve the high-temperature cycle performance at 45 ℃. This is probably because the chain ether solvent has lower viscosity and melting point, and after being added into the electrolyte, the surface tension of the electrolyte can be reduced, the wettability of the electrolyte to the high-compaction positive and negative plates and the diaphragm is improved, the liquid absorption amount of the battery cell is improved, and the activation time of the battery cell is reduced; the chain ether solvent is mixed with other common carbonate solvents to form an electrolyte solvent with extremely low eutectic point, so that the electrolyte of the lithium ion battery can still keep a liquid phase at low temperature, and the utilization efficiency of activated substances is improved. On the other hand, the chain ether is a weak polar solvent and has weak coordination capacity, so that the coordination structure of the original carbonate solvent and lithium ions is not changed after the addition, thereby retaining the characteristic of high stability of the carbonate electrolyte, but effectively reducing the viscosity of the electrolyte, increasing the dissociation degree of the lithium ions and greatly improving the conductivity of the electrolyte.
It is evident from comparative examples 1-5 that the dynamic performance of the cell is improved with decreasing compacted density while maintaining the solvent system unchanged. This shows that reduced compacted density can improve diffusion of lithium ions, and simultaneously improve wettability of the electrode sheet and electrolyte, so that kinetics and cycle life of the lithium ion battery are improved.
As is apparent from comparative examples 6 to 10, when the compacted density of the lithium iron phosphate positive electrode sheet is not changed, the degree of improvement of DCR at-20C, low-temperature discharge and 2C high-rate charge-discharge performance of the battery gradually decreases with decrease of the content of the weak polar alkyl chain ether, but the 45℃ cycle performance is improved and then deteriorated, probably because the HOMO value of the chain ether is high, oxidation resistance is not high, and gas generation is deteriorated with excessively high content, resulting in deterioration of 45℃ cycle.
As can be seen from comparative examples 1 to 18, when D/W was 0.3.ltoreq.D.ltoreq.0.6, the improvement effect on dynamics was more remarkable without deteriorating the high temperature cycle performance.
As is clear from comparative examples 11, 14 to 18, the different weakly polar alkyl chain cyclic ethers have comparable effects of improving low temperature kinetics (-DCR at 20 ℃, low temperature discharge, and 2C high rate charge-discharge performance) and cycle performance.
Table 2: lithium ion battery preparation parameters and test results of examples 1, 19-29 and comparative example 2
Note that: in Table 2, D is the compacted density (unit: g/cm) of the positive electrode material layer on the positive electrode sheet 3 ) W is the mass fraction of diluent in the organic solvent (unit: and (3%) and X is the mass fraction of Mg element in the positive electrode active material (unit: ppm).
As can be seen from a comparison of example 29 and comparative example 2 in table 2, the addition of the chain ether compound of the present invention to the electrolyte can improve the low-temperature discharge capacity retention rate and the high-temperature cycle capacity retention rate. As is clear from comparison of example 1 and example 29, the use of Mg-doped lithium iron phosphate as the positive electrode material is advantageous in further improving the low-temperature discharge capacity retention rate and the high-temperature cycle capacity retention rate. As is clear from examples 1 and 19-28, when the lithium ion battery further satisfies 30.ltoreq.X/W.ltoreq.6000, the lithium ion battery has better performance, and shows higher retention of high-temperature cycle capacity and retention of low-temperature discharge capacity. This is probably because the positive electrode doping element Mg can form a solid solution with other elements, bringing the impurity level between the conduction band and the forbidden band of lithium iron phosphate to provide electron conductivity of lithium iron phosphate. Meanwhile, the lattice defect of the material can be increased by doping, the diffusion channel of lithium ions is expanded, and the resistance of lithium ion intercalation/deintercalation is reduced, so that the ion and electron conductivity of lithium iron phosphate is improved. In addition, the diluent alkyl chain ether is not oxidation-resistant, so that the stability of an anode interface is poor, and the structural fracture is caused; the positive electrode doped element Mg can occupy the Li position after the positive electrode is delithiated to stabilize the positive electrode structure, alleviate the structural distortion in the circulation process, ensure excellent low-temperature performance and simultaneously improve the high-temperature stability of the system.
While the invention has been described with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (10)

1. An electrolyte of a lithium ion battery is characterized by comprising an organic solvent and lithium salt, wherein the organic solvent comprises a chain ether compound shown in a formula I and a carbonate solvent:
R 1 -O-(R 2 -O) n -R 3
I
in the formula I, n is an integer more than or equal to 1;
each R is 2 Each independently selected from linear or branched C 1 -C 6 Alkylene and straight-chain or branched C 2 -C 6 Alkenylene radicals, each R 2 Optionally one or more H on carbon atoms of (c) may be substituted with a group selected from: alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkyloxy, heterocyclyl, heterocyclyloxy, aryl, aryloxy, heteroaryl, nitro, ester, halogen, and aldehyde groups;
R 1 and R is 3 Each independently selected from hydrogen atoms, C 1 -C 6 Alkyl, C 3 -C 6 Cycloalkyl, ternary to six membered heterocyclyl, C 2 -C 6 Alkenyl and C 2 -C 6 One or more of the alkynyl groups, the R 1 And R is 3 Optionally one or more H on carbon atoms of (c) may be substituted with a group selected from: alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkyloxy, heterocyclyl, heterocyclyloxy, aryl, aryloxy, heteroaryl, nitro, ester, halogen, and aldehyde groups.
2. Electrolyte according to claim 1, wherein in formula I n is an integer between 1 and 6, preferably 1; each R is 2 Each independently selected from linear or branched C 1 -C 4 Alkylene and straight-chain or branched C 2 -C 4 Alkenylene, preferably selected from linear or branched C 2 -C 4 An alkylene group; r is R 1 And R is 3 Each independently selected from linear or branched C 1 -C 6 Alkyl groups, preferably selected from methyl and ethyl;
preferably, the chain ether compound is selected from one or more of ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol diethyl ether, 1, 4-butanediol dimethyl ether, 1, 4-butanediol diethyl ether and 1, 4-butanediol methyl ethyl ether.
3. Electrolyte according to claim 1, wherein the chain ether compound accounts for < 10% by mass of the organic solvent, preferably more than or equal to 3% and less than 10%.
4. The electrolyte of claim 1 wherein the carbonate-based solvent comprises at least one cyclic carbonate comprising one or more selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate, and gamma-butyrolactone and at least one chain carbonate comprising one or more selected from the group consisting of dimethyl carbonate, diethyl carbonate, and ethylmethyl carbonate.
5. The electrolyte of claim 1, wherein,
the concentration of the lithium salt in the electrolyte is 0.5-2mol/L; and/or
The lithium salt is selected from one or more of lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide, lithium bis (oxalato) borate, lithium difluorooxalato borate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, lithium fluoride and lithium trifluoromethane sulfonate.
6. A lithium ion battery, characterized in that it comprises a positive electrode sheet, a negative electrode sheet and the electrolyte of any one of claims 1-5;
preferably, the positive electrode active material contained in the positive electrode sheet includes lithium iron phosphate.
7. The lithium-ion battery of claim 6, wherein the positive electrode sheet comprises a positive electrode material layer having a compacted density of D g/cm 3 The chain ether compound accounts for W% of the organic solvent, and the following relation is satisfied by D and W: D/W is more than or equal to 0.3 and less than or equal to 0.6.
8. The electrolyte according to claim 6, wherein the positive electrode active material contained in the positive electrode sheet is lithium iron phosphate containing Mg element, the weight content of Mg element is X ppm, X is 350-20000, the weight percentage of the chain ether compound in the organic solvent is w%, and X and W satisfy the following relationship: X/W is more than or equal to 30 and less than or equal to 6000.
9. The lithium ion battery according to claim 6, wherein the negative electrode active material contained in the negative electrode sheet is selected from lithium metal, graphite, mesophase carbon spheres, hard carbon, soft carbon, silicon-carbon composite, li-Sn alloy, li-Sn-O alloy, spinel-structured lithiated TiO 2 -Li 4 Ti 5 O 12 And one or more of Li-Al alloys.
10. The lithium-ion battery of claim 6, wherein the lithium-ion battery is a cylindrical lithium-ion battery, a soft-pack lithium-ion battery, or an aluminum-shell lithium-ion battery.
CN202210470455.4A 2022-04-28 2022-04-28 Lithium ion battery electrolyte and battery thereof Pending CN117013083A (en)

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