CN110797544A - High-performance lithium primary battery and preparation method thereof - Google Patents
High-performance lithium primary battery and preparation method thereof Download PDFInfo
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- CN110797544A CN110797544A CN201910943266.2A CN201910943266A CN110797544A CN 110797544 A CN110797544 A CN 110797544A CN 201910943266 A CN201910943266 A CN 201910943266A CN 110797544 A CN110797544 A CN 110797544A
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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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The invention discloses a high-performance lithium primary battery and a preparation method thereof, aiming at the structural characteristic that carbon fluoride of the lithium primary battery is taken as a positive electrode, fluoroether is added into electrolyte as an additive, and the fluoroether contains fluorine elements, so that the fluoroether and the carbon fluoride positive electrode have better affinity, the wettability of the electrolyte to a positive electrode material is increased, the transmission of electrons and lithium ions is facilitated, the multiplying power performance of the battery is improved, the battery can still maintain a higher discharge platform and discharge capacity under high current density, and the high-performance lithium primary battery has high power density and high energy density. The electrolyte system overcomes the technical problem that the actual power density and the energy density of the existing lithium primary battery are low, and is expected to be applied to the energy storage system of the lithium primary battery in a large scale; the preparation method is simple and feasible and is easy to realize.
Description
[ technical field ] A method for producing a semiconductor device
The invention belongs to the technical field of electrochemical energy storage, and particularly relates to a high-performance lithium primary battery and a preparation method thereof.
[ background of the invention ]
Lithium primary batteries are widely applied to various weaponry such as various electronic instruments and communication equipment, wherein lithium-carbon fluoride (Li/CFx) primary batteries are a lithium/solid positive electrode system with the highest specific energy at present and are one of the lithium primary batteries which are used in the market at first. The theoretical mass specific energy can reach 2180Wh/kg, the working temperature range is wide, the device can work in the range of minus 40 to 170 ℃, the self-discharge is small, and the storage life reaches more than 10 years.
In the discharge process of the battery, the CFx is converted into conductive carbon, the conductive carbon is of an amorphous microporous structure, the conductivity of the battery is increased to a certain extent, the internal resistance of the battery is reduced, the stable discharge voltage is kept, the discharge efficiency of the battery is improved, and therefore the battery system has a high voltage platform retention rate. But simultaneously, the discharge product is also oxidized into LiF crystals and gradually enters the micropores of the conductive carbon, so that the ion diffusion of the anode material is hindered, the electronic conductivity is reduced, the high-rate discharge of the battery cannot be realized, and the power density and the energy density cannot reach theoretical values.
Electrolyte is a key factor affecting the electrochemical performance of lithium-carbon fluoride (Li/CFx, x ═ 0-1) primary batteries. The components and the proportion of the electrolyte determine whether the electrolyte has good conductivity, wettability, chemical stability, electrochemical stability, high-temperature performance and the like, so that the performance of the battery is influenced.
[ summary of the invention ]
The present invention is directed to overcoming the above-mentioned disadvantages of the prior art and providing a high-performance lithium primary battery and a method for preparing the same. The method is used for solving the problems that the lithium-carbon fluoride primary battery can not discharge at high rate and has lower power density and energy density.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
a high-performance lithium primary battery comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the positive plate and the negative plate are separated by the diaphragm; the positive plate, the negative plate and the diaphragm are soaked in the electrolyte; the negative plate is made of lithium, and the positive plate is made of carbon fluoride;
the electrolyte comprises an electrolyte matrix and an additive, wherein the electrolyte matrix comprises an organic solvent and electrolyte salt; the additive is fluoroether, and the structural formula of the fluoroether is as follows:
R1-C-O-C-R2
wherein R is1And R2Are all hydrocarbyl groups.
The invention is further improved in that:
preferably, R1And R2Each of which is a hydrocarbon group having 1 to 12 carbon atoms and having some or all of its hydrogen atoms substituted with fluorine.
Preferably, the volume of the additive accounts for 0.001-75% of the sum of the volume of the electrolyte matrix and the volume of the additive.
Preferably, the volume of the additive accounts for 10-50% of the sum of the volume of the electrolyte matrix and the volume of the additive.
Preferably, the electrolyte salt is lithium perchlorate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bistrifluoromethanesulfonimide or lithium trifluoromethanesulfonate.
Preferably, the concentration of the electrolyte salt in the electrolyte matrix is 0.1-5 mol/L.
Preferably, the organic solvent is one or a mixture of ethylene glycol dimethyl ether, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate.
A preparation method of a high-performance lithium primary battery comprises the following specific processes: mixing an organic solvent and an additive to obtain a mixed solution A; adding electrolyte salt into the mixed solution A, and uniformly stirring to obtain an electrolyte;
and (3) sequentially assembling the positive plate, the electrolyte, the diaphragm and the lithium plate into the battery to prepare the high-performance lithium primary battery.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a high-performance lithium primary battery, aiming at the structural characteristic that carbon fluoride of the lithium primary battery is taken as a positive electrode, fluoroether is added into electrolyte as an additive, and the fluoroether contains fluorine elements, so that the fluoroether and the carbon fluoride positive electrode have better affinity, the wettability of the electrolyte to a positive electrode material is increased, the transmission of electrons and lithium ions is facilitated, the multiplying power performance of the battery is improved, the battery can still maintain a higher discharge platform and discharge capacity under high current density, and the high-performance lithium primary battery has high power density and high energy density. And the fluoroether has lower viscosity, so that the viscosity of the electrolyte can be reduced, the migration of lithium ions is facilitated, and the rate capability of the lithium primary battery is improved. Meanwhile, the fluoroether has excellent high-temperature performance, can ensure that the lithium primary battery has higher discharge platform and discharge capacity at high temperature, keeps good rate performance, and has higher power density and energy density. The electrolyte system overcomes the technical problem of low actual power density and energy density of the existing lithium primary battery, and is expected to be applied to the energy storage system of the lithium primary battery on a large scale.
Experiments prove that the lithium-carbon fluoride (Li/CF) adopting the electrolyte of the inventionX，X＝0-1) The discharge plateau of the primary cell is significantly higher than that of lithium-carbon fluoride (Li/CF) without additiveX，X＝0-1) The primary battery is high, and the rate capability and the high-temperature performance are obviously improved; lithium-carbon fluoride (Li/CF) prepared by using electrolyte of the inventionX，X＝0-1) The discharge plateau of the primary battery is 2.265V, the power density is 6795W/kg, the energy density is 1391Wh/kg under the conditions of room temperature (25 ℃) and high current density (3000mA/g), and the discharge plateau is higher than that of electrolyte without additives; the energy density at high temperature (55 ℃) and high current density (3000mA/g) is 1475Wh/kg, which is 3.5 times that of electrolyte without additive, because the fluoroether improves the wettability of the electrolyte to the fluorocarbon anode and improves the high-temperature performance.
The invention also discloses a preparation method of the high-performance lithium primary battery, and the method only needs to mix the organic solvent, the electrolyte salt and the additive according to the conventional electrolyte preparation method to prepare the electrolyte; the lithium primary battery is prepared by assembling the anode, the cathode, the diaphragm and the electrolyte of the battery according to the conventional method, and the preparation method is simple and has strong operability.
[ description of the drawings ]
FIG. 1 is a schematic of an electrolyte without additives to lithium-carbon fluoride (Li/CF)xX ═ 1) discharge curves at different current densities in primary cells at room temperature (25 ℃).
FIG. 2 is a schematic representation of an electrolyte without additives to lithium-carbon fluoride (Li/CF)xX ═ 1) discharge curves at different current densities at high temperature (55 ℃) in primary cells.
FIG. 3 is a schematic representation of an electrolyte containing additives to lithium-carbon fluoride (Li/CF)xX ═ 1) discharge curves at different current densities in primary cells at room temperature (25 ℃).
FIG. 4 shows the composition without additivesIn lithium-carbon fluoride (Li/CF)xX ═ 1) discharge curves at different current densities at high room temperature (55 ℃) in primary cells.
[ detailed description ] embodiments
The invention is described in further detail below with reference to the following figures and specific examples:
the invention discloses a high-performance lithium primary battery and a preparation method thereof, wherein the battery is lithium-carbon fluoride (Li/CF)X,X＝0-1) Primary battery, lithium-carbon fluoride (Li/CF)X,X＝0-1) The primary battery consists of a positive plate, a negative plate, a diaphragm for separating the positive plate from the negative plate and electrolyte. Wherein, the positive plate comprises a positive current collector and a positive material coated on the surface of the positive current collector, and the positive material is Carbon Fluoride (CF)X，X＝0-1) (ii) a The negative plate is a metal lithium plate; the diaphragm is a PP-PE-PP composite diaphragm; the positive plate, the negative plate and the diaphragm are soaked in the electrolyte.
The electrolyte comprises an electrolyte matrix and an additive; the electrolyte matrix comprises an organic solvent and electrolyte salt, wherein the concentration of the electrolyte salt in the electrolyte matrix is 0.1-5 mol/L; the additive is fluoroether, the volume of the additive accounts for 0.001-75% of the total volume of the electrolyte matrix and the additive, namely the volume of the additive in the high-performance electrolyte of the lithium primary battery accounts for 0.001-75%, preferably 10-50%.
The organic solvent is one or a mixture of more of ethylene glycol dimethyl ether (DME), Ethylene Carbonate (EC), Propylene Carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC).
The electrolyte salt is lithium perchlorate (LiClO for short)4) Lithium hexafluorophosphate (LiPF for short)6) Lithium tetrafluoroborate (LiBF for short)4) Lithium bistrifluoromethanesulfonimide (LiTFSI for short), lithium bistrifluoromethanesulfonimide (LiFSI for short) or lithium trifluoromethanesulfonimide (LiCF for short)3SO3)。
The electrolyte additive has the following structural formula:
R1-C-O-C-R2
wherein R is1And R2Are all hydrocarbyl groups.
Preferably, R1And R2The hydrocarbon group has 1 to 12 carbon atoms and some or all of the hydrogens are replaced with fluorine.
The specific process of the battery preparation is as follows:
step 1, preparing a positive plate
Fluorinating Carbon (CF) as a positive electrode active materialX，X＝0-1) Mixing conductive carbon black serving as a conductive agent and polyvinylidene fluoride (PVDF) serving as a binder in a mass ratio of 8:1:1, adding a proper amount of N-methylpyrrolidone (NMP for short) for ball milling to prepare anode slurry, wherein the amount of the added NMP can ensure sufficient fluidity of the anode slurry, so that the anode slurry is uniformly coated on an aluminum foil of an anode current collector, the coating thickness is 200 micrometers, and then, carrying out vacuum drying for 12 hours at 80 ℃ to obtain an anode plate.
Step 2, preparing electrolyte
According to the volume content of the additive in the electrolyte, firstly mixing an organic solvent and the additive to obtain a mixed solution A, and adding electrolyte salt into the mixed solution A according to the concentration of the electrolyte salt in an electrolyte matrix to obtain the electrolyte.
Step 3, preparation of lithium-Carbon Fluoride (CF)X，X＝0-1) Primary cell
Placing the positive plate in the center of the positive shell, dripping a proper amount of electrolyte (40-50uL), covering the positive plate with the diaphragm, dripping a proper amount of electrolyte (40-50uL), sequentially stacking the lithium plate, the gasket and the elastic sheet, and finally buckling the negative shell to complete the lithium-carbon fluoride (Li/CF)X,X＝0-1) Preparation of primary battery, noted c.
The electrolyte can improve the multiplying power performance of the battery and improve the high-temperature performance according to the following principle: lithium-carbon fluoride (Li/CF) using the electrolyte of the present inventionX,X＝0-1) When the fluoroether is used as the additive, the primary battery is favorable for increasing the wettability of the electrolyte to the carbon fluoride anode, so that the battery can still maintain a higher discharge platform and discharge capacity under high current density, and further has high power density and high energy density. Meanwhile, the fluoroether has excellent high-temperature performance, so that the battery still has good rate at high temperatureAnd (4) performance.
Experiments prove that the lithium-Carbon Fluoride (CF) adopting the electrolyte of the inventionXX-0-1) primary cell has a discharge plateau that is significantly higher than additive-free lithium-carbon fluoride (Li/CF)X,X＝0-1) The primary battery is high, and the rate capability and the high-temperature performance are obviously improved; lithium-carbon fluoride (Li/CF) prepared by using electrolyte of the inventionX,X＝0-1) The discharge plateau of the primary battery is 2.265V, the power density is 6795W/kg, the energy density is 1391Wh/kg under the conditions of room temperature (25 ℃) and high current density (3000mA/g), and the discharge plateau is higher than that of electrolyte without additives; the energy density at high temperature (55 ℃) and high current density (3000mA/g) is 1475Wh/kg, which is 3.5 times that of electrolyte without additive, because the fluoroether improves the wettability of the electrolyte to the fluorocarbon anode and improves the high-temperature performance.
The present invention will be further described with reference to comparative examples and examples.
Comparative example 1
1) Preparation of Positive electrode sheet a
Fluorinating Carbon (CF) as a positive electrode active materialx,x＝1) Mixing conductive carbon black serving as a conductive agent and polyvinylidene fluoride (PVDF) serving as a binder in a mass ratio of 8:1:1, adding a proper amount of N-methylpyrrolidone (NMP for short) for ball milling to prepare anode slurry, wherein the amount of the added NMP can ensure sufficient fluidity of the anode slurry, so that the anode slurry is uniformly coated on an aluminum foil of an anode current collector, the coating thickness is 200 micrometers, and then, carrying out vacuum drying for 12 hours at 80 ℃ to obtain an anode sheet a.
2) Preparation of electrolyte b
Mixing ethylene glycol dimethyl ether (DME) and Propylene Carbonate (PC) according to the volume ratio of DME to PC to 1:1 to obtain an organic solvent, and adding electrolyte salt lithium perchlorate (LiClO for short) into the organic solvent4)，LiClO4The concentration of the electrolyte in the mixed solution of the organic solvent and the electrolyte salt is 1mol/L, namely the conventional electrolyte and is marked as b.
3) Lithium-carbon fluoride (Li/CF)xX ═ 1) preparation of Primary Battery c
Placing the positive plate in the center of the positive shell, dripping 40uL of conventional electrolyte b, covering the positive plate with the diaphragm, and drippingAdding 40uL of electrolyte, sequentially stacking the lithium sheet, the gasket and the elastic sheet, and finally buckling the negative electrode shell to finish the lithium-carbon fluoride (Li/CF)X,X＝1) Preparation of primary battery, noted c.
Lithium-carbon fluoride (Li/CF) at preparation of comparative example 1xX ═ 1) electrochemical performance testing of primary cell c, test cases were as follows:
condition 1
Lithium-carbon fluoride (Li/CF)xX ═ 1) primary cell c was left to stand at room temperature (25 ℃ C.) for 8 hours and discharged to 1.5V with a constant current having a current density of 10 mA/g.
Condition 2
Lithium-carbon fluoride (Li/CF)xX ═ 1) primary cell c was left to stand at room temperature (25 ℃ C.) for 8 hours and discharged to 1.5V with a constant current having a current density of 50 mA/g.
Condition 3
Lithium-carbon fluoride (Li/CF)xX ═ 1) primary cell c was left to stand at room temperature (25 ℃ C.) for 8 hours and discharged to 1.5V with a constant current having a current density of 100 mA/g.
Condition 4
Lithium-carbon fluoride (Li/CF)xX ═ 1) primary cell c was left to stand at room temperature (25 ℃ C.) for 8 hours and discharged to 1.5V with a constant current having a current density of 500 mA/g.
Condition 5
Lithium-carbon fluoride (Li/CF)xX ═ 1) primary cell c was left to stand at room temperature (25 ℃ C.) for 8 hours and discharged to 1.5V with a constant current having a current density of 1000 mA/g.
Condition 6
Lithium-carbon fluoride (Li/CF)xX ═ 1) primary cell c was left to stand at room temperature (25 ℃ C.) for 8 hours and discharged to 1.5V with a constant current having a current density of 2000 mA/g.
Condition 7
Lithium-carbon fluoride (Li/CF)xX ═ 1) primary cell c was left to stand at room temperature (25 ℃ C.) for 8 hours and discharged to 1.5V with a constant current having a current density of 3000 mA/g.
Condition 8
Lithium-carbon fluoride (Li/CF)xX ═ 1) primary cell c was left to stand at room temperature (25 ℃ C.) for 8 hours and discharged to 1.5V with a constant current having a current density of 5000 mA/g.
Comparative example 1 the discharge curves of the cells of condition 6 to condition 8 are shown in fig. 1.
Condition 9
Lithium-carbon fluoride (Li/CF)xX ═ 1) primary cell c was left to stand at high temperature (55 ℃) for 8 hours and discharged to 1.5V with a constant current having a current density of 10 mA/g.
Condition 10
Lithium-carbon fluoride (Li/CF)xX ═ 1) primary cell c was left to stand at high temperature (55 ℃) for 8 hours and discharged to 1.5V with a constant current having a current density of 50 mA/g.
Condition 11
Lithium-carbon fluoride (Li/CF)xX ═ 1) primary cell c was left to stand at high temperature (55 ℃) for 8 hours and discharged to 1.5V with a constant current having a current density of 100 mA/g.
Condition 12
Lithium-carbon fluoride (Li/CF)xX ═ 1) primary cell c was left to stand at high temperature (55 ℃) for 8 hours and discharged to 1.5V with a constant current having a current density of 500 mA/g.
Condition 13
Lithium-carbon fluoride (Li/CF)xX ═ 1) primary cell c was left to stand at high temperature (55 ℃) for 8 hours and discharged to 1.5V with a constant current having a current density of 1000 mA/g.
Condition 14
Lithium-carbon fluoride (Li/CF)xX ═ 1) primary cell c was left to stand at high temperature (55 ℃) for 8 hours and discharged to 1.5V with a constant current having a current density of 2000 mA/g.
Condition 15
Lithium-carbon fluoride (Li/CF)xX ═ 1) primary cell c was left to stand at high temperature (55 ℃) for 8 hours and discharged to 1.5V with a constant current having a current density of 3000 mA/g.
Condition 16
Lithium-carbon fluoride (Li/CF)xX ═ 1) primary cell c was left to stand at high temperature (55 ℃) for 8 hours and discharged to 1.5V with a constant current having a current density of 5000 mA/g.
The processes and parameters not specified in this comparative example were the same as those in comparative example 1.
The discharge curves of the cells of conditions 14 to 16 are shown in fig. 2.
Example 1
DME: TTE: PC 2:2:1 by volume ratio DME, TTE andPC to obtain a mixed solution A, and adding an electrolyte salt LiClO into the mixed solution A4(ii) a TTE occupies 40% of the volume of the electrolyte matrix and the total volume of the additive, and the concentration of electrolyte salt in the electrolyte matrix is 1mol/L, so as to obtain a new electrolyte; the structural formula of the additive is as follows:
assembling lithium-carbon fluoride (Li/CF) with the electrolyteX,X＝1) A primary battery; the processes and parameters not specified in this example were the same as those in comparative example 1; the cells obtained in this example were subjected to electrochemical performance tests using different conditions, the conditions and conditions of the tests being as follows:
condition 1
Lithium-carbon fluoride (Li/CF)xX ═ 1) primary cell c was left to stand at room temperature (25 ℃ C.) for 8 hours and discharged to 1.5V with a constant current having a current density of 10 mA/g.
Condition 2
Lithium-carbon fluoride (Li/CF)xX ═ 1) primary cell c was left to stand at room temperature (25 ℃ C.) for 8 hours and discharged to 1.5V with a constant current having a current density of 50 mA/g.
Condition 3
Lithium-carbon fluoride (Li/CF)xX ═ 1) primary cell c was left to stand at room temperature (25 ℃ C.) for 8 hours and discharged to 1.5V with a constant current having a current density of 100 mA/g.
Condition 4
Lithium-carbon fluoride (Li/CF)xX ═ 1) primary cell c was left to stand at room temperature (25 ℃ C.) for 8 hours and discharged to 1.5V with a constant current having a current density of 500 mA/g.
Condition 5
Lithium-carbon fluoride (Li/CF)xX ═ 1) primary cell c was left to stand at room temperature (25 ℃ C.) for 8 hours and discharged to 1.5V with a constant current having a current density of 1000 mA/g.
Condition 6
Lithium-carbon fluoride (Li/CF)xX ═ 1) primary cell c was left to stand at room temperature (25 ℃ C.) for 8 hours and discharged to 1.5V with a constant current having a current density of 2000 mA/g.
Condition 7
Subjecting lithium-fluorocarbons (C)Li/CFxX ═ 1) primary cell c was left to stand at room temperature (25 ℃ C.) for 8 hours and discharged to 1.5V with a constant current having a current density of 3000 mA/g.
Condition 8
Lithium-carbon fluoride (Li/CF)xX ═ 1) primary cell c was left to stand at room temperature (25 ℃ C.) for 8 hours and discharged to 1.5V with a constant current having a current density of 5000 mA/g.
The discharge curves of the batteries prepared in example 1 under conditions 6 to 8 are shown in fig. 3.
Condition 9
Lithium-carbon fluoride (Li/CF)xX ═ 1) primary cell c was left to stand at high temperature (55 ℃) for 8 hours and discharged to 1.5V with a constant current having a current density of 10 mA/g.
Condition 10
Lithium-carbon fluoride (Li/CF)xX ═ 1) primary cell c was left to stand at high temperature (55 ℃) for 8 hours and discharged to 1.5V with a constant current having a current density of 50 mA/g.
Condition 11
Lithium-carbon fluoride (Li/CF)xX ═ 1) primary cell c was left to stand at high temperature (55 ℃) for 8 hours and discharged to 1.5V with a constant current having a current density of 100 mA/g.
Condition 12
Lithium-carbon fluoride (Li/CF)xX ═ 1) primary cell c was left to stand at high temperature (55 ℃) for 8 hours and discharged to 1.5V with a constant current having a current density of 500 mA/g.
Condition 13
Lithium-carbon fluoride (Li/CF)xX ═ 1) primary cell c was left to stand at high temperature (55 ℃) for 8 hours and discharged to 1.5V with a constant current having a current density of 1000 mA/g.
Condition 14
Lithium-carbon fluoride (Li/CF)xX ═ 1) primary cell c was left to stand at high temperature (55 ℃) for 8 hours and discharged to 1.5V with a constant current having a current density of 2000 mA/g.
Condition 15
Lithium-carbon fluoride (Li/CF)xX ═ 1) primary cell c was left to stand at high temperature (55 ℃) for 8 hours and discharged to 1.5V with a constant current having a current density of 3000 mA/g.
Condition 16
Lithium-carbon fluoride (Li/CF)xX ═ 1) primary cell c was allowed to stand at high temperature (55 ℃ C.)Standing for 8h, and discharging to 1.5V with constant current with current density of 5000 mA/g.
The discharge curves of the cells of conditions 14 to 16 are shown in fig. 4.
As can be seen from comparison between FIG. 1 and FIG. 3, the discharging platform is obviously increased and the power density and energy density are also increased after fluoroether is added into the electrolyte at high current density (2000mA/g and above) at room temperature (25 ℃); as can be seen from the comparison of FIG. 2 and FIG. 4, the discharging platform is also increased significantly after fluoroether is added into the electrolyte at high current density at high temperature (55 ℃), and the power density and energy density are also increased by more than 0.2V. This shows that after the fluoroether is added, the wettability of the electrolyte to the anode material is obviously improved, the rate capability is improved, and the high-temperature performance of the electrolyte is also improved. The electrochemical performance of the above battery is shown in table 1 below:
TABLE 1 lithium-fluorocarbons (Li/CF)xX ═ 1) results of electrochemical performance tests of primary batteries
As a result, it can be seen that fluoroethers were added as electrolyte additives for lithium-carbon fluoride (Li/CF)xAnd x is 1), the rate performance of the battery is improved at room temperature (25 ℃) and high temperature (55 ℃), and the improvement is more obvious especially when the current density is more than 1000 mA/g. Before fluoroether is not added as an electrolyte additive, the battery has almost no discharge capacity at the current density of 5000mA/g, after fluoroether is added as the electrolyte additive, the battery reaches more than 350mAh/g at the current density of 5000mA/g, the rate capability is obviously improved, and the power density and the energy density are also obviously improved.
Example 2
Mixing PC and an additive according to the volume ratio of 5:5 to obtain a mixed solution A, and adding an electrolyte salt LiBF into the mixed solution A4(ii) a WhereinThe additive occupies 50 percent of the volume of the electrolyte matrix and the total volume of the additive, and the concentration of electrolyte salt in the electrolyte matrix is 4mol/L, so as to obtain new electrolyte; the structural formula of the additive is as follows:
assembling lithium-carbon fluoride (Li/CF) with the electrolyte0.5) A primary battery; the processes and parameters not specified in this example were the same as those in comparative example 1.
Example 3
Mixing DMC and an additive according to the volume ratio of 8:2 to obtain a mixed solution A, and adding electrolyte salt LiTFSi into the mixed solution A; wherein the additive occupies 20 percent of the volume of the electrolyte matrix and the total volume of the additive, and the concentration of the electrolyte salt in the electrolyte matrix is 0.2mol/L, so as to obtain a new electrolyte; the structural formula of the additive is as follows:
assembling lithium-carbon fluoride (Li/CF) with the electrolyte0.3) A primary battery; the processes and parameters not specified in this example were the same as those in comparative example 1.
Example 4
Mixing DEC and an additive according to the volume ratio of 7:3 to obtain a mixed solution A, and adding an electrolyte salt LiFeSi into the mixed solution A; wherein the additive occupies 30 percent of the volume of the electrolyte matrix and the total volume of the additive, and the concentration of the electrolyte salt in the electrolyte matrix is 0.1mol/L, so as to obtain a new electrolyte; the structural formula of the additive is as follows:
assembling lithium-carbon fluoride (Li/CF) with the electrolyte0.6) A primary battery; the processes and parameters not specified in this example were the same as those in comparative example 1.
Example 5
According to the volume ratio of 9Mixing EMC and additives at a ratio of 9.9:0.1 to obtain a mixed solution A, and adding an electrolyte salt LiClO to the mixed solution A4(ii) a Wherein the additive occupies 0.001% of the volume of the electrolyte matrix and the total volume of the additive, and the concentration of the electrolyte salt in the electrolyte matrix is 0.5mol/L, so as to obtain a new electrolyte; the structural formula of the additive is as follows:
assembling lithium-carbon fluoride (Li/CF) with the electrolyte0.1) A primary battery; the processes and parameters not specified in this example were the same as those in comparative example 1.
Example 6
Mixing EC and additive according to the volume ratio of 1:3 to obtain a mixed solution A, and adding electrolyte salt LiPF into the mixed solution A6(ii) a Wherein the additive occupies 75% of the volume of the electrolyte matrix and the total volume of the additive, and the concentration of the electrolyte salt in the electrolyte matrix is 2mol/L, so as to obtain a new electrolyte; the structural formula of the additive is as follows:
assembling lithium-carbon fluoride (Li/CF) with the electrolyte0.8) A primary battery; the processes and parameters not specified in this example were the same as those in comparative example 1.
Example 7
Mixing EC, PC and additives according to the volume ratio of 3:3:14 to obtain a mixed solution A, and adding electrolyte salt LiBF into the mixed solution A4(ii) a Wherein the additive occupies 70% of the volume of the electrolyte matrix and the total volume of the additive, and the concentration of the electrolyte salt in the electrolyte matrix is 5mol/L, so as to obtain a new electrolyte; the structural formula of the additive is as follows:
assembling a lithium-carbon fluoride (Li/CF) primary battery with the electrolyte; the processes and parameters not specified in this example were the same as those in comparative example 1.
Example 8
Mixing DMC, DEC and an additive according to the volume ratio of 1:3:6 to obtain a mixed solution A, and adding an electrolyte salt LiTFSi into the mixed solution A; wherein the additive occupies 60 percent of the volume of the electrolyte matrix and the total volume of the additive, and the concentration of the electrolyte salt in the electrolyte matrix is 2.5mol/L, so as to obtain a new electrolyte; the structural formula of the additive is as follows:
assembling lithium-carbon fluoride (Li/CF) with the electrolyte0.9) A primary battery; the processes and parameters not specified in this example were the same as those in comparative example 1.
Example 9
Mixing EMC, DEC and an additive according to the volume ratio of 3:4:3 to obtain a mixed solution A, and adding an electrolyte salt LiTSi into the mixed solution A; wherein the additive occupies 30 percent of the volume of the electrolyte matrix and the total volume of the additive, and the concentration of the electrolyte salt in the electrolyte matrix is 3.5mol/L, so as to obtain a new electrolyte; the structural formula of the additive is as follows:
assembling lithium-carbon fluoride (Li/CF) with the electrolyte0.5) A primary battery; the processes and parameters not specified in this example were the same as those in comparative example 1.
Example 10
Mixing DMC, DEC, EMC and additives according to the volume ratio of 4:3:2:1 to obtain a mixed solution A, and adding an electrolyte salt LiCF into the mixed solution A3SO3(ii) a Wherein the additive occupies 10 percent of the volume of the electrolyte matrix and the total volume of the additive, and the concentration of the electrolyte salt in the electrolyte matrix is 4.5mol/L, so as to obtain a new electrolyte; the structural formula of the additive is as follows:
assembling a lithium-carbon fluoride (Li/CF) primary battery with the electrolyte; the processes and parameters not specified in this example were the same as those in comparative example 1.
Example 11
Mixing DMC, PC, EC and additive according to the volume ratio of 11:8:1 to obtain a mixed solution A, and adding an electrolyte salt LiClO into the mixed solution A4(ii) a Wherein the additive occupies 5 percent of the volume of the electrolyte matrix and the total volume of the additive, and the concentration of the electrolyte salt in the electrolyte matrix is 5mol/L, so as to obtain a new electrolyte; the structural formula of the additive is as follows:
assembling a lithium-carbon fluoride (Li/CF) primary battery with the electrolyte; the processes and parameters not specified in this example were the same as those in comparative example 1.
Example 12
Mixing EMC and additives according to a volume ratio of 99.9:0.1 to obtain a mixed solution A, and adding an electrolyte salt LiClO into the mixed solution A4(ii) a Wherein the additive occupies 0.001% of the volume of the electrolyte matrix and the total volume of the additive, and the concentration of the electrolyte salt in the electrolyte matrix is 0.5mol/L, so as to obtain a new electrolyte; the additive is BTFE, and the structural formula of the additive is as follows:
assembling lithium-carbon fluoride (Li/CF) with the electrolyte0.5) A primary battery; the processes and parameters not specified in this example were the same as those in comparative example 1.
Example 13
Mixing EC and additive according to the volume ratio of 1:3 to obtain a mixed solution A, and adding electrolyte salt LiPF into the mixed solution A6(ii) a Wherein the additive occupies 75% of the volume of the electrolyte matrix and the total volume of the additive, and the concentration of the electrolyte salt in the electrolyte matrix is 2mol/L, so as to obtain a new electrolyte; the additive is FE2, and the structural formula is as follows:
assembling a lithium-carbon fluoride (Li/CFx, x ═ 1) primary battery with the electrolyte; the processes and parameters not specified in this example were the same as those in comparative example 1.
Example 14
Mixing EC, PC and additives according to the volume ratio of 3:3:14 to obtain a mixed solution A, and adding electrolyte salt LiBF into the mixed solution A4(ii) a Wherein the additive occupies 70% of the volume of the electrolyte matrix and the total volume of the additive, and the concentration of the electrolyte salt in the electrolyte matrix is 5mol/L, so as to obtain a new electrolyte; the additive is T1216, and the structural formula of the additive is as follows:
assembling a lithium-carbon fluoride (Li/CFx, x ═ 1) primary battery with the electrolyte; the processes and parameters not specified in this example were the same as those in comparative example 1.
Example 15
Mixing DMC, DEC and an additive according to the volume ratio of 1:3:6 to obtain a mixed solution A, and adding an electrolyte salt LiTFSi into the mixed solution A; wherein the additive occupies 60 percent of the volume of the electrolyte matrix and the total volume of the additive, and the concentration of the electrolyte salt in the electrolyte matrix is 2.5mol/L, so as to obtain a new electrolyte; the additive is T3057, and the structural formula of the additive is as follows:
assembling lithium-carbon fluoride (Li/CF) with the electrolyte0.8) A primary battery; the processes and parameters not specified in this example were the same as those in comparative example 1.
Example 16
Mixing EMC, DEC and an additive according to the volume ratio of 3:4:3 to obtain a mixed solution A, and adding an electrolyte salt LiTSi into the mixed solution A; wherein the additive occupies 30 percent of the volume of the electrolyte matrix and the total volume of the additive, and the concentration of the electrolyte salt in the electrolyte matrix is 3.5mol/L, so as to obtain a new electrolyte; the additive is T7301, and the structural formula is as follows:
assembling lithium-carbon fluoride (Li/CF) with the electrolyte0.2) A primary battery; the processes and parameters not specified in this example were the same as those in comparative example 1.
Example 17
Mixing DMC, DEC, EMC and additives according to the volume ratio of 4:3:2:1 to obtain a mixed solution A, and adding an electrolyte salt LiCF into the mixed solution A3SO3(ii) a Wherein the additive occupies 10 percent of the volume of the electrolyte matrix and the total volume of the additive, and the concentration of the electrolyte salt in the electrolyte matrix is 4.5mol/L, so as to obtain a new electrolyte; the additive is T5202, and the structural formula is as follows:
assembling a lithium-carbon fluoride (Li/CFx, x ═ 1) primary battery with the electrolyte; the processes and parameters not specified in this example were the same as those in comparative example 1.
The electrolyte increases the wettability of the electrolyte to the carbon fluoride anode by introducing fluoroether and by the affinity of the fluorine-containing liquid and the fluorine-containing solid, so that the battery can still maintain a higher discharge platform and discharge capacity under high current density, and has high power density and high energy density. Meanwhile, the fluoroether has excellent high-temperature performance, so that the battery still has good rate performance at high temperature.
The above examples are only illustrations of several examples of the present invention, but it is understood that other fluoroether additives can be used in the examples to achieve the effects of the present invention.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. A high-performance lithium primary battery is characterized by comprising a positive plate, a negative plate, a diaphragm and electrolyte, wherein the positive plate and the negative plate are separated by the diaphragm; the positive plate, the negative plate and the diaphragm are soaked in the electrolyte; the negative plate is made of lithium, and the positive plate is made of carbon fluoride;
the electrolyte comprises an electrolyte matrix and an additive, wherein the electrolyte matrix comprises an organic solvent and electrolyte salt; the additive is fluoroether, and the structural formula of the fluoroether is as follows:
R1-C-O-C-R2
wherein R is1And R2Are all hydrocarbyl groups.
2. The high performance lithium primary battery of claim 1, wherein R is1And R2Each of which is a hydrocarbon group having 1 to 12 carbon atoms and having some or all of its hydrogen atoms substituted with fluorine.
3. The primary lithium battery of claim 1, wherein the additive is present in an amount of 0.001 to 75% by volume based on the sum of the volume of the electrolyte matrix and the volume of the additive.
4. The primary lithium battery of claim 1, wherein the additive comprises 10% to 50% by volume of the total volume of the electrolyte matrix and the additive.
5. The high performance lithium primary battery of claim 1 wherein the electrolyte salt is lithium perchlorate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bistrifluoromethanesulfonylimide, or lithium trifluoromethanesulfonate.
6. The high-performance lithium primary battery according to claim 1, wherein the concentration of the electrolyte salt in the electrolyte matrix is 0.1 to 5 mol/L.
7. The lithium primary battery of claim 1, wherein the organic solvent is one or more of ethylene glycol dimethyl ether, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate.
8. A preparation method of a high-performance lithium primary battery is characterized by comprising the following specific steps: mixing an organic solvent and an additive to obtain a mixed solution A; adding electrolyte salt into the mixed solution A, and uniformly stirring to obtain an electrolyte;
and (3) sequentially assembling the positive plate, the electrolyte, the diaphragm and the lithium plate into the battery to prepare the high-performance lithium primary battery.
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