CN114552010B - Additive for lithium metal battery, electrolyte and lithium metal battery - Google Patents
Additive for lithium metal battery, electrolyte and lithium metal battery Download PDFInfo
- Publication number
- CN114552010B CN114552010B CN202210173804.6A CN202210173804A CN114552010B CN 114552010 B CN114552010 B CN 114552010B CN 202210173804 A CN202210173804 A CN 202210173804A CN 114552010 B CN114552010 B CN 114552010B
- Authority
- CN
- China
- Prior art keywords
- lithium
- lithium metal
- additive
- metal battery
- electrolyte
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- H01M10/0567—Liquid materials characterised by the additives
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/40—Alloys based on alkali metals
- H01M4/405—Alloys based on lithium
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides an additive for a lithium metal battery, an electrolyte and the lithium metal battery, wherein the additive is a phosphoramide compound containing a-P-F group. The additive can form a stable protective film on the surface of a lithium metal cathode by bonding with lithium metal, and the film is rich in LiF and Li 3 N，LiN x O y ，LiP x O y And the like, wherein a plurality of heteroatoms such as phosphorus, nitrogen, fluorine, oxygen and the like have electronegativity and have attraction to lithium ions, and the SEI film formed after the decomposition product is deposited on the surfaces of the anode and the cathode is beneficial to the lithium ions to pass through, so that the DCR of the SEI film is effectively improved, the rate capability of the lithium metal battery is further improved, and the electrochemical adverse reaction caused by lithium dendrites in the lithium metal battery is weakened. In addition, the oxidation potential of the-P-F group is higher, so that the oxidation resistance of the additive can be improved after the additive is introduced, and the additive is beneficial to inhibiting the oxidative decomposition of the electrolyte under a 4.55V high-voltage system, thereby improving the cycle performance of the lithium metal battery.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, particularly relates to an electrolyte, and more particularly relates to an additive for a lithium metal battery, the electrolyte and the lithium metal battery.
Background
With the rapid development of the electrical, electronic, communication, and computer industries, the demand for secondary batteries having high performance and high stability is rapidly increasing. In particular, in accordance with the trend toward weight reduction, thickness reduction, size reduction, and portability of batteries and electronic products, weight reduction and size reduction of secondary batteries as core members are also required. In addition, due to the demand for new energy supply sources caused by environmental pollution problems and oil consumption, there is an increasing demand for the development of electric vehicles capable of solving such a demand. Among secondary batteries, lithium secondary batteries having a long cycle life, being light in weight, and exhibiting high energy density and operating potential have recently received attention.
The lithium secondary battery has a structure in which an electrode assembly including a cathode, an anode, and a separator disposed between the cathode and the anode is laminated or wound, and is constructed by inserting the electrode assembly into a battery case and injecting a nonaqueous electrolytic solution into the interior thereof. In this case, the capacity of the lithium secondary battery differs according to the type of the electrode active material, and the capacity at the time of actual driving cannot be secured by a sufficient capacity as much as the theoretical capacity, and thus such a battery has not been commercialized.
In order to obtain a lithium secondary battery having a high capacity, metal materials having high storage capacity characteristics by alloying reaction with lithium, such as silicon (4200 mAh/g) and tin (990 mAh/g), are used as anode active materials. However, when a metal such as silicon and tin is used as an anode active material, it expands in volume by about 4 times during charging for alloying with lithium and contracts again during discharging. Since a large volume change of the electrode assembly repeatedly occurs during the charge/discharge process, the active material is gradually micronized and is released from the electrode, and thus the capacity is rapidly reduced, thereby making it difficult to ensure stability and reliability, and thus causing a failure in commercialization.
Since lithium metal has an excellent theoretical capacity of 3860mAh/g and a low potential of-3.045V with respect to a Standard Hydrogen Electrode (SHE) as compared to the above negative electrode active material, thereby enabling a battery having a high capacity and a high energy density to be obtained, much research has been conducted on a Lithium Metal Battery (LMB) using lithium metal as a negative electrode active material of a lithium secondary battery.
However, in the case of a lithium metal battery, lithium metal is liable to react with an electrolyte, impurities and a lithium salt due to its high chemical/electrochemical reactivity, and a Solid Electrolyte Interphase (SEI) is formed on the surface of an electrode, and such a solid electrolyte interphase causes a local current density difference, thereby forming dendrites on the surface of lithium metal. The lithium dendrite not only shortens the life of the lithium secondary battery, but also causes short circuit and dead lithium in the battery, thereby increasing physical and chemical instability of the lithium secondary battery, reducing the capacity of the battery, shortening the cycle life, and adversely affecting the stability of the battery. In addition, the solid electrolyte interphase is thermally unstable, so that the charge/discharge process of the battery may be continuously performed, or the solid electrolyte interphase may gradually collapse due to increased electrochemical energy and thermal energy, particularly during high-temperature storage in a full charge state. Due to the collapse of the intermediate phase of the solid electrolyte, a side reaction in which the exposed surface of the lithium metal is decomposed by a direct reaction with the electrolyte solvent continuously occurs, and thus the resistance of the anode increases, and the charge/discharge efficiency of the battery decreases. In addition, there are problems as follows: during the formation of the intermediate phase of the solid electrolyte, the solvent of the electrolyte is consumed, and the life of the battery is shortened due to by-products, gases, etc. generated during various side reactions such as the formation and collapse of the intermediate phase of the solid electrolyte and the decomposition of the electrolyte.
Korean patent No. KR2016-106169610A discloses that the cycle characteristics of a 4.4V lithium cobaltate material can be improved by a combination of fluorine-substituted ethers and non-fluorine-substituted ethers additives. In addition, chinese patent CN202010965195 discloses that the cyclic lithium phosphate amide salt has high stability when applied to an electrolyte, and an SEI film formed during charge and discharge cycles is more favorable for lithium ions to pass through, thereby improving the electrical performance of a 4.5v ncm523 battery. However, the above-described improvement effect is not sufficient, and therefore, it is required to develop a novel electrolyte for stabilizing a lithium metal interface as a negative electrode in a 4.55V lithium metal battery.
Disclosure of Invention
In order to solve the above problems, it is an object of the present invention to provide an additive for a lithium metal battery, an electrolyte and a lithium metal battery thereof, which can improve electrochemical performance of the lithium metal battery, particularly, can improve capacity and cycle life of a high voltage lithium metal battery.
In order to achieve the purpose, the invention provides an additive for a lithium metal battery, which is a phosphoramide compound containing a-P-F group.
The lithium metal battery additive comprises a phosphoramide compound containing a-P-F group, the phosphoramide compound can form a bond with lithium metal to form a stable protective film on the surface of a lithium metal cathode, and the film is rich in LiF and Li 3 N，LiN x O y ，LiP x O y And the like, wherein a plurality of heteroatoms such as phosphorus, nitrogen, fluorine, oxygen and the like have electronegativity and have attraction to lithium ions, and the SEI film formed after the decomposition product is deposited on the surfaces of the positive electrode and the negative electrode is beneficial to the lithium ions to pass through, so that the DCR (resistance) of the SEI film is effectively improved, the rate capability of the lithium metal battery is further improved, and the electrochemical adverse reaction caused by lithium dendrites in the lithium metal battery is weakened. In addition, the compound contains a-P-F group, the oxidation potential of the structure is higher, the oxidation resistance of the additive can be improved after the compound is introduced, and the compound is helpful for inhibiting the oxidative decomposition of the electrolyte under a 4.55V high-voltage system, thereby improving the cycle performance of the lithium metal battery.
The invention provides an electrolyte for a lithium metal battery in a second aspect, which comprises a lithium salt, a non-aqueous organic solvent and an additive, wherein the additive comprises the additive for the lithium metal battery.
The electrolyte for the lithium metal battery comprises a phosphoramide compound containing a-P-F group, and the phosphoramide compound can improve the DCR (resistance) of an SEI film, so that the rate capability of the battery can be improved, the oxidation potential is higher, and the cycle performance of the lithium metal battery can be improved.
The invention provides a lithium metal battery, which comprises a positive electrode material, a negative electrode material and an electrolyte, wherein the electrolyte is the electrolyte, the negative electrode material is lithium metal or lithium alloy, and the maximum charging voltage is 4.55V.
The cathode material of the invention is lithium metal or lithium alloy, so the capacity of the battery is higher, and the electrolyte comprises a phosphoramide compound containing-P-F group, thereby further improving the multiplying power and the cycle performance of the battery.
Detailed Description
The additive for the lithium metal battery is a phosphamide compound containing a-P-F group. The phosphoramide compound containing-P-F group is shown as a structural formula I or a structural formula II, wherein R 1 Is a fluorine atom or a fluorohydrocarbon, R 2 And R 3 Each independently selected from at least one of a hydrocarbon group, a phenyl group, an ester group, a silicon group, and a fluorocarbon.
Further, R 1 Is fluorine atom or C 1 -C 3 Of a fluorinated hydrocarbon of 2 And R 3 Each independently selected from C 1 -C 3 Alkyl, phenyl, C 2 -C 3 Ester group of (A), trimethylsilyl group and C 1 -C 3 At least one fluorinated hydrocarbon of (a). More preferably, R 1 Is a fluorine atom, R 2 And R 3 Each independently selected from at least one of methyl, ethyl, phenyl, methyl formate, trimethylsilyl and fluoromethyl. The phosphamide compound containing the-P-F group is preferably at least one of the compounds 1 to 6, preferably the compound 4 and the compound 5.
The electrolyte for the lithium metal battery comprises a lithium salt, a non-aqueous organic solvent and an additive, wherein the additive comprises the additive for the lithium metal battery. Wherein, the phosphamide compound containing-P-F group accounts for 0.1 to 5 percent of the total mass of the lithium salt, the non-aqueous organic solvent and the additive, and is preferably 0.05 to 1 percent. When the content thereof is less than 0.05%, an SEI film cannot be uniformly formed on the surface of the lithium metal anode, and thus a desired effect cannot be obtained. In contrast, when the content exceeds 5%, an unnecessary reaction may occur at the time of driving of the lithium metal battery, so that the performance of the lithium metal battery may be deteriorated. The content of the phosphoramide compound containing the-P-F group can be, but is not limited to, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%.
Wherein the lithium salt is selected from LiCl, liBr, liI and LiClO 4 、LiBF 4 、LiPF 6 、LiCF 3 SO 3 、LiCF 3 CO 2 、LiC 4 BO 8 、LiAsF 6 、LiSbF 6 、LiAlCl 4 、CH 3 SO 3 Li、CF 3 SO 3 Li、(CF 3 SO 2 ) 2 NLi、(C 2 F 5 SO 2 ) 2 NLi、(SO 2 F) 2 NLi、(CF 3 SO 2 ) 3 At least one of Cli and lithium chloroborane. Preferably (CF) 3 SO 2 ) 2 NLi (lithium bis (trifluoromethanesulfonylimide), liTFSI) and (SO) 2 F) 2 NLi (lithium bis (fluorosulfonyl) imide, liFSI) due to the anion-SO of LiTFSI 2 F 3 And anion-SO of LiFSI 2 The F group has high reactivity to lithium, decomposition products mainly comprise LiF, and the high surface energy of LiF and lithium metal is favorable for inhibiting the growth of lithium dendrites. Meanwhile, liF has low electronic conductivity and high electrochemical stability, and can effectively passivate the surface of the lithium metal cathode, so that the lithium metal cathode is protected. Therefore, the film forming performance of LiTFSI and LiFSI on the surface of the lithium metal negative electrode is better, and the lithium metal negative electrode can be protected more effectively and the growth of lithium dendrites can be inhibited. The lithium salt accounts for 6.5 to 15.5% of the total mass of the lithium salt, the nonaqueous organic solvent and the additive, and may be, but is not limited to, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 15.5%, in consideration of ionic conductivity, solubility and the like in the electrolyte. The concentration may be 0.1 to 4.0M, preferably 0.5 to 2.0M. When the concentration of the lithium salt is less than 0.1M, it is difficult to ensure ion conductivity suitable for battery driving. In contrast, when the concentration exceeds 4.0M, the viscosity of the electrolyte increases to lower the mobility of lithium ions, and the lithium salt itself is divided intoThe decomposition reaction may increase to cause deterioration of the battery performance.
The organic solvent is at least one of chain carbonate, cyclic carbonate, carboxylic ester, lactone and ether compounds. Wherein the chain carbonate may be at least one of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), ethyl Methyl Carbonate (EMC), methyl propyl carbonate (PMC) and ethyl propyl carbonate (PEC). The cyclic carbonate may be at least one of Ethylene Carbonate (EC), propylene Carbonate (PC), fluoroethylene carbonate (FEC), butylene carbonate, and pentylene carbonate. The carboxylic acid ester may be at least one of methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, and propyl propionate. The lactone may be at least one of gamma-butyrolactone, gamma-valerolactone, gamma-caprolactone, sigma-valerolactone and epsilon-caprolactone. The ether compound may be at least one of dimethyl ether, diethyl ether, dipropyl ether, methyl ethyl ether, methyl propyl ether, ethyl propyl ether, dimethoxy ethane, diethoxy ethane, methoxyethoxy ethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol methyl ethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol methyl ethyl ether, polyethylene glycol dimethyl ether, polyethylene glycol diethyl ether, polyethylene glycol methyl ethyl ether, 1, 3-dioxolane, tetrahydrofuran, and 2-methyltetrahydrofuran. In addition, the organic solvent may further comprise N-methylpyrrolidone, dimethylsulfoxide or sulfolane.
The additive of the invention can also comprise at least one of Ethylene Sulfite (ES), vinylene Carbonate (VC), vinyl Ethylene Carbonate (VEC), 1,3 Propane Sultone (PS) and vinyl sulfate (DTD) besides the phosphoramide compound containing-P-F group, and the total content of the latter accounts for 0.1-10% of the sum of the mass of the lithium salt, the non-aqueous organic solvent and the additive. In addition, the lithium salt, the non-aqueous organic solvent and the additive can also comprise 0.01 to 1 percent of nitric acid compound by mass, and the nitric acid compound can be lithium nitrate (LiNO) 3 ) Potassium nitrate (KNO) 3 ) Cesium nitrate (CsNO) 3 ) Magnesium nitrate (Mg (NO) 3 ) 2 ) Barium nitrate (Ba (NO) 3 ) 2 ) Lithium nitrite (LiNO) 2 )、Potassium nitrite (KNO) 2 ) Cesium nitrite (CsNO) 2 )。
A third aspect of the present invention provides a lithium metal battery comprising a positive electrode material, a negative electrode material and an electrolyte, wherein the electrolyte is the aforementioned electrolyte, the negative electrode material is lithium metal or a lithium alloy, and the maximum charging voltage is 4.55V. Further, the anode material is a lithium cobaltate material, a nickel cobalt manganese oxide or a nickel cobalt aluminum oxide. Preferably, the lithium cobaltate material is doped and coated modified lithium cobaltate, and the chemical formula of the nickel-cobalt-manganese oxide is LiNi x Co y Mn z M (1-x-y-z) O 2 The chemical formula of the nickel-cobalt-aluminum oxide is LiNi x Co y Al z N (1-x-y-z) O 2 Wherein M is at least one of Mg, cu, zn, al, sn, B, ga, cr, sr, V and Ti, N is at least one of Mn, mg, cu, zn, sn, B, ga, cr, sr, V and Ti, and x is more than or equal to 0.6 and less than or equal to x<1，0<y<1，0<z<1，x+y+z≤1。
The objects, technical solutions and advantages of the present invention are further illustrated by the following specific examples, which should not be construed as limiting the invention in any way. The examples, in which specific conditions are not specified, may be conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used are conventional products available on the market, not indicated by the manufacturer.
Example 1
(1) Preparing an electrolyte: in a vacuum glove box with the moisture content of less than 1ppm under the argon atmosphere, methyl ethyl carbonate (EMC) and fluoroethylene carbonate (FEC) are mixed according to the weight ratio of EMC: FEC =50, then the additives are added, the lithium salt is added after dissolution and full stirring, and the electrolyte is obtained after uniform mixing.
(2) Preparation of the positive electrode: reacting LiNi 0.8 Mn 0.1 Co 0.1 O 2 And uniformly mixing the PVDF adhesive and the SuperP conductive agent according to the mass ratio of 95.
(3) Preparing a diaphragm: polyethylene (PE) having a thickness of about 15 μm was used as the separator.
(4) Preparation of a negative electrode: compounding metal lithium on a current collector copper foil with the thickness of about 10 mu m by a physical rolling method, adjusting the pressure of a roller to coat lithium on two sides of the copper current collector, and controlling the thickness of the coated lithium to be about 35 mu m to obtain the lithium-copper composite belt negative electrode. Then, after being cut into pieces and cut, the cut pieces are placed in a dry argon atmosphere glove box for storage and standby.
(5) Preparation of lithium metal battery: and sequentially stacking the anode, the isolating membrane and the lithium copper composite strip cathode, and then stacking according to the requirement. And welding the tabs, placing the welded tabs into an aluminum plastic film for battery external packaging, injecting the prepared electrolyte into the dried bare cell, sequentially carrying out vacuum packaging, standing, formation (charging to 3.6V at a constant current of 0.05C and then charging to 3.9V at a constant current of 0.1C), shaping, capacity testing and other processes, and finally obtaining the soft package lithium metal battery with 1 Ah.
The electrolyte formulations of examples 2 to 12 and comparative examples 1 to 3 are shown in table 1, and the procedure for preparing the electrolyte and the procedure for preparing the battery are the same as in example 1.
TABLE 1 electrolyte Components of the examples
The lithium metal batteries manufactured in examples 1 to 12 and comparative examples 1 to 3 were subjected to rate and cycle tests, respectively, under the following specific test conditions, and the performance test results are shown in table 2.
(1) Rate capability test
The lithium metal batteries of examples 1 to 12 and comparative examples 1 to 3 were constant-current charged at 0.5C to 4.55V at 25 deg.C, and thenCharging at constant voltage until the current is 0.05C, discharging at constant current of 0.5C to 3.0V, repeating the charging and discharging for 3 times, and discharging at the last time 0 . Charging to 4.55V at constant current of 0.5C, charging at constant voltage to 0.05C, discharging to 3.0V at constant current of 2C, and discharging at discharge capacity of C 1 . Capacity retention = C1/C0 x 100%
(2) Cycle performance test
The lithium metal batteries of examples 1 to 12 and comparative examples 1 to 2 were subjected to 0.5C/0.5C charge and discharge (battery discharge capacity C0) at 25 ℃ once with an upper limit voltage of 4.55V, and then subjected to 0.5C/0.5C charge and discharge at room temperature for 300 weeks (battery discharge capacity C1), capacity retention ratio = (C1/C0) × 100%
Table 2 results of performance test of each example
As is apparent from the results shown in Table 2, examples 1 to 12 are superior to comparative examples 1 to 3 in rate capability and cycle performance, and examples 1 to 12 have phosphoramides containing-P-F groups, which can form a stable protective film on the surface of a lithium metal negative electrode by bonding with lithium metal, the film being rich in LiF and Li 3 N，LiN x O y ，LiP x O y And the like, wherein a plurality of heteroatoms such as phosphorus, nitrogen, fluorine, oxygen and the like are charged negatively and have attraction to lithium ions, and the SEI film formed after the decomposition product is deposited on the surfaces of the positive electrode and the negative electrode is beneficial to the lithium ions to pass through, so that the DCR (resistance) of the SEI film is effectively improved, the rate capability of the lithium metal battery is further improved, and the electrochemical adverse reaction caused by lithium dendrites in the lithium metal battery is weakened. In addition, the compound contains a-P-F group, the oxidation potential of the structure is high, the oxidation resistance of the additive can be improved after the compound is introduced, and the compound is helpful for inhibiting the oxygen of the electrolyte under a 4.55V high-voltage systemAnd decomposing, thereby improving the cycle performance of the lithium metal battery. In comparative example 2, although a phosphoramide compound was also added, P was completely substituted with diethylamino, and a-P-F group was not present, so that it was difficult to suppress oxidative decomposition of the electrolyte of a lithium metal battery in a 4.55V high voltage system, and the cycle performance was not good.
Comparative examples 1 to 2, and examples 5 to 8, it is understood that the rate performance of the lithium metal battery is better when the compounds 5 and 6 are used, which may be related to having more electron withdrawing groups.
As can be seen by comparing example 2 and example 10, the cycle performance of the lithium metal battery is increased when the lithium salt is LiFSI, which is probably due to LiFSI anion-SO 2 The F group has higher reactivity to lithium, the decomposition product is mainly LiF, and the high surface energy of LiF and lithium metal is favorable for inhibiting the growth of lithium dendrites. Meanwhile, liF has low electronic conductivity and high electrochemical stability, and can effectively passivate the surface of the lithium metal cathode, so that the lithium metal cathode is protected.
Comparing example 2 and example 11, it is known that when the solvent contains a high content of FEC, the cycle performance of the lithium metal battery is improved, which is probably because the introduction of fluoroethylene carbonate FEC molecules with stronger affinity to lithium ions participates in the lithium ion solvation shell layer to reduce the lithium ion desolvation energy barrier, thereby reducing the polarization of the lithium ion deposition and desorption process. Meanwhile, FEC molecules coordinated with lithium ions are preferentially decomposed on the surface of the lithium metal to form an SEI film rich in LiF, so that the diffusion energy barrier of the lithium ions in the SEI film can be reduced, and the lithium metal is induced to be uniformly deposited.
It can be seen from comparison example 12 and comparison example 3 that the addition of VEC on the basis of the phosphoramide compounds containing-P-F groups improves the rate and cycle performance, especially the cycle performance, because the LUMO level of VEC is very low, it can be preferentially reduced and decomposed on the surface of the lithium metal negative electrode to generate a polycarbonate-rich SEI film, and the polycarbonate material has cohesiveness and flexibility, which can help the SEI film adapt to the stress caused by the volume change of the lithium metal negative electrode, and improve the stability of the SEI film.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (2)
1. A lithium metal battery comprises a positive electrode material, a negative electrode material and an electrolyte, and is characterized in that the positive electrode material is a lithium cobaltate material, a nickel cobalt manganese oxide or a nickel cobalt aluminum oxide, the negative electrode material is a lithium metal or a lithium alloy, the highest charging voltage is 4.55V, the electrolyte comprises a lithium salt, a nonaqueous organic solvent and an additive, the organic solvent is at least one of chain carbonate, cyclic carbonate, carboxylate, lactone and ether compounds, the additive comprises a phosphoramide compound containing a-P-F group, the phosphoramide compound containing the-P-F group accounts for 0.1 to 5 percent of the sum of the mass of the lithium salt, the nonaqueous organic solvent and the additive, the lithium salt accounts for 6.5 to 15.5 percent of the sum of the mass of the lithium salt, the nonaqueous organic solvent and the additive, the phosphoramide compound containing the-P-F group is at least one of compounds 1 to 5,
compound 1 Compound 2 Compound 3
Compound 4 compound 5.
2. The lithium metal battery of claim 1, wherein the lithium salt is selected from the group consisting of LiCl, liBr, liI, liClO 4 、LiBF 4 、LiPF 6 、LiCF 3 SO 3 、LiCF 3 CO 2 、LiC 4 BO 8 、LiAsF 6 、LiSbF 6 、LiAlCl 4 、CH 3 SO 3 Li、CF 3 SO 3 Li、(CF 3 SO 2 ) 2 NLi、(C 2 F 5 SO 2 ) 2 NLi、(SO 2 F) 2 NLi、(CF 3 SO 2 ) 3 At least one of Cli and lithium chloroborane.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210173804.6A CN114552010B (en) | 2022-02-23 | 2022-02-23 | Additive for lithium metal battery, electrolyte and lithium metal battery |
| PCT/CN2022/097318 WO2023159796A1 (en) | 2022-02-23 | 2022-06-07 | Additive for lithium metal battery, electrolyte and lithium metal battery thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210173804.6A CN114552010B (en) | 2022-02-23 | 2022-02-23 | Additive for lithium metal battery, electrolyte and lithium metal battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114552010A CN114552010A (en) | 2022-05-27 |
| CN114552010B true CN114552010B (en) | 2022-12-09 |
Family
ID=81676706
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210173804.6A Active CN114552010B (en) | 2022-02-23 | 2022-02-23 | Additive for lithium metal battery, electrolyte and lithium metal battery |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN114552010B (en) |
| WO (1) | WO2023159796A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114552010B (en) * | 2022-02-23 | 2022-12-09 | 珠海市赛纬电子材料股份有限公司 | Additive for lithium metal battery, electrolyte and lithium metal battery |
| CN115863768B (en) * | 2023-02-22 | 2023-04-25 | 安徽盟维新能源科技有限公司 | Electrolyte and lithium metal battery containing same |
| US20250015365A1 (en) * | 2023-07-03 | 2025-01-09 | International Business Machines Corporation | Rechargeable battery with an sei protective layer on the surface of a metal anode and method for making same |
| CN117558987B (en) * | 2024-01-12 | 2024-05-03 | 江苏天鹏电源有限公司 | Lithium ion battery electrolyte and lithium ion battery |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108808087A (en) * | 2018-05-04 | 2018-11-13 | 惠州市大道新材料科技有限公司 | A kind of electrolyte containing phosphorimide lithium and the battery using the electrolyte |
| CN110299562A (en) * | 2019-07-17 | 2019-10-01 | 珠海市赛纬电子材料股份有限公司 | A kind of new lithium salts additive and its non-aqueous electrolyte for lithium ion cell |
| CN111786020A (en) * | 2020-07-20 | 2020-10-16 | 香河昆仑化学制品有限公司 | Non-aqueous electrolyte containing fluoro phosphoric acid amide salt and lithium ion battery |
| CN112186248A (en) * | 2020-09-30 | 2021-01-05 | 香河昆仑化学制品有限公司 | Lithium ion battery non-aqueous electrolyte and lithium ion battery |
| CN112467207A (en) * | 2019-09-09 | 2021-03-09 | 宁德时代新能源科技股份有限公司 | Electrolyte and lithium metal battery containing same |
| CN112952196A (en) * | 2020-09-15 | 2021-06-11 | 比亚迪股份有限公司 | Cyclic lithium phosphoramidate salt, preparation method thereof, electrolyte additive, electrolyte and battery |
| CN113113669A (en) * | 2021-04-09 | 2021-07-13 | 珠海市赛纬电子材料股份有限公司 | Electrolyte additive, non-aqueous electrolyte containing electrolyte additive and lithium ion battery |
| CN113889667A (en) * | 2021-12-08 | 2022-01-04 | 新乡华锐锂电新能源有限公司 | High-voltage electrolyte adaptive to lithium cobaltate battery capable of being charged quickly and application of high-voltage electrolyte |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5484078B2 (en) * | 2010-01-06 | 2014-05-07 | 東ソ−・エフテック株式会社 | Nonaqueous electrolyte containing fluorine-containing phosphoric ester amide |
| EP2697453B1 (en) * | 2011-04-11 | 2018-10-10 | Shenzhen Capchem Technology Co. Ltd. | Non-aqueous electrolytic solutions and electrochemical cells comprising the same |
| KR102025969B1 (en) * | 2012-06-15 | 2019-09-26 | 토소 에프테크 인코퍼레이티드 | METHOD FOR STABILIZING LiPF6, ELECTROLYTE SOLUTION FOR NONAQUEOUS SECONDARY BATTERIES HAVING EXCELLENT THERMAL STABILITY, AND NONAQUEOUS SECONDARY BATTERY HAVING EXCELLENT THERMAL STABILITY |
| JP6665396B2 (en) * | 2015-02-19 | 2020-03-13 | セントラル硝子株式会社 | Electrolyte for non-aqueous electrolyte battery and non-aqueous electrolyte battery using the same |
| JP5835514B1 (en) * | 2015-05-27 | 2015-12-24 | 宇部興産株式会社 | Lithium salt compound, and non-aqueous electrolyte, lithium ion secondary battery, and lithium ion capacitor using the same |
| WO2018190304A1 (en) * | 2017-04-10 | 2018-10-18 | セントラル硝子株式会社 | Method for producing phosphoryl imide salt, method for producing nonaqueous electrolyte solution containing said salt, and method for producing nonaqueous secondary battery |
| CN108232168B (en) * | 2018-01-19 | 2020-06-09 | 河北力滔电池材料有限公司 | Modified lithium iron phosphate composite material and preparation method thereof |
| US11881558B2 (en) * | 2020-01-09 | 2024-01-23 | Apple Inc. | Electrolytes for lithium-containing battery cells |
| CN113549111A (en) * | 2020-04-24 | 2021-10-26 | 北京康派森医药科技有限公司 | A kind of preparation method of tenofovir alafenamide fumarate impurity |
| CN114552010B (en) * | 2022-02-23 | 2022-12-09 | 珠海市赛纬电子材料股份有限公司 | Additive for lithium metal battery, electrolyte and lithium metal battery |
-
2022
- 2022-02-23 CN CN202210173804.6A patent/CN114552010B/en active Active
- 2022-06-07 WO PCT/CN2022/097318 patent/WO2023159796A1/en active Application Filing
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108808087A (en) * | 2018-05-04 | 2018-11-13 | 惠州市大道新材料科技有限公司 | A kind of electrolyte containing phosphorimide lithium and the battery using the electrolyte |
| CN110299562A (en) * | 2019-07-17 | 2019-10-01 | 珠海市赛纬电子材料股份有限公司 | A kind of new lithium salts additive and its non-aqueous electrolyte for lithium ion cell |
| CN112467207A (en) * | 2019-09-09 | 2021-03-09 | 宁德时代新能源科技股份有限公司 | Electrolyte and lithium metal battery containing same |
| CN111786020A (en) * | 2020-07-20 | 2020-10-16 | 香河昆仑化学制品有限公司 | Non-aqueous electrolyte containing fluoro phosphoric acid amide salt and lithium ion battery |
| CN112952196A (en) * | 2020-09-15 | 2021-06-11 | 比亚迪股份有限公司 | Cyclic lithium phosphoramidate salt, preparation method thereof, electrolyte additive, electrolyte and battery |
| CN112186248A (en) * | 2020-09-30 | 2021-01-05 | 香河昆仑化学制品有限公司 | Lithium ion battery non-aqueous electrolyte and lithium ion battery |
| CN113113669A (en) * | 2021-04-09 | 2021-07-13 | 珠海市赛纬电子材料股份有限公司 | Electrolyte additive, non-aqueous electrolyte containing electrolyte additive and lithium ion battery |
| CN113889667A (en) * | 2021-12-08 | 2022-01-04 | 新乡华锐锂电新能源有限公司 | High-voltage electrolyte adaptive to lithium cobaltate battery capable of being charged quickly and application of high-voltage electrolyte |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2023159796A1 (en) | 2023-08-31 |
| CN114552010A (en) | 2022-05-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4033074B2 (en) | Secondary battery electrolyte and secondary battery using the same | |
| CN114552010B (en) | Additive for lithium metal battery, electrolyte and lithium metal battery | |
| JP4379567B2 (en) | Secondary battery electrolyte and secondary battery using the same | |
| US7662519B2 (en) | Non-aqueous electrolyte secondary battery | |
| JP4465968B2 (en) | Secondary battery electrolyte and secondary battery using the same | |
| JP2009252545A (en) | Non-aqueous electrolyte and non-aqueous electrolyte secondary battery | |
| JP5305446B2 (en) | Nonaqueous electrolyte and nonaqueous electrolyte secondary battery using the same | |
| KR102023677B1 (en) | Electrolyte for Secondary Battery and Secondary Battery Comprising the Same | |
| KR102277754B1 (en) | Electrolyte Solution for Secondary Battery and Secondary Battery Comprising the Same | |
| CN114497743B (en) | Electrolyte applied to alkali metal battery and alkali metal battery thereof | |
| JP4968614B2 (en) | Secondary battery electrolyte and secondary battery using the same | |
| JP2007328992A (en) | Nonaqueous electrolyte and nonaqueous electrolyte secondary battery using the same | |
| JP2005203342A (en) | Secondary battery | |
| JP5300054B2 (en) | Nonaqueous electrolyte and nonaqueous electrolyte secondary battery using the same | |
| CN111934015B (en) | Non-aqueous electrolyte of lithium ion battery and lithium ion battery containing non-aqueous electrolyte | |
| CN112151861A (en) | Battery cathode surface protection composition, electrolyte and application thereof | |
| JP4701601B2 (en) | Electrolytic solution for lithium secondary battery and lithium secondary battery using the same | |
| CN113113668B (en) | Electrolyte additive, non-aqueous electrolyte containing electrolyte additive and lithium ion battery | |
| JP4265169B2 (en) | Secondary battery electrolyte and secondary battery using the same | |
| CN110970663A (en) | Non-aqueous electrolyte and lithium ion battery | |
| JP4525018B2 (en) | Electrolytic solution for lithium secondary battery and lithium secondary battery using the same | |
| KR20090106993A (en) | Non-aqueous electrolyte and non-aqueous electrolyte secondary battery using same | |
| CN116315106A (en) | Nonaqueous electrolyte and lithium ion battery | |
| CN119050476A (en) | Nonaqueous electrolyte and lithium ion battery | |
| EP4369456A1 (en) | Electrolyte additive for secondary battery, non-aqueous electrolyte for lithium secondary battery comprising same, and lithium secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |