CN111293299B - Modified metal lithium negative electrode battery and preparation method thereof - Google Patents
Modified metal lithium negative electrode battery and preparation method thereof Download PDFInfo
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- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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Abstract
The invention provides a modified metal lithium cathode battery and a preparation method thereof, wherein the modified metal lithium cathode battery comprises an anode, an electrolyte and a modified metal lithium cathode, the metal lithium cathode is reacted with acetic acid steam under the anhydrous and oxygen-free conditions to obtain the metal lithium cathode covered with a lithium acetate passive film, the growth of lithium dendrites in the circulation process is inhibited by the presence of the passive film, and the battery performance is improved; and because lithium acetate is synthesized in situ, the binding force between the passivation film and lithium metal is enhanced, the cycle performance of the battery is greatly improved, and the problem of weak binding force of a lithium metal SEI film is solved.
Description
Technical Field
The invention relates to a modified metal lithium negative electrode battery and a preparation method thereof.
Background
Lithium has advantages as a negative electrode material that other materials cannot compete with. The density of the metallic lithium is very small and is only 0.534g/cm3, and the gram capacity of the metallic lithium is as high as 3860mAh/g which is ten times of that of a graphite cathode (372mAh/g), and the use of the metallic lithium as the cathode can reduce the consumption of cathode materials so as to improve the energy density of the battery. Based on the advantages, the metal lithium is the most promising high-energy lithium ion battery cathode material.
However, lithium metal negative electrodes have serious problems that prevent their practical use, mainly safety and stability. In the lithium electrode cycle process, lithium dendrites are easily formed and grown on the surface of the lithium negative electrode, so that the internal short circuit of the battery is caused, and the local overheating combustion and even explosion of the battery are caused. This is mainly due to uneven deposition and dissolution of lithium ions on the surface of the lithium negative electrode, resulting in uneven electrode surface, resulting in uneven local current flow, and thus formation of lithium dendrites and "dead lithium" during the deposition and dissolution of lithium. Although metallic lithium reacts with the electrolyte during the first charge and discharge to form a solid electrolyte phase (SEI) that conducts ions but not electrons, which prevents the metallic lithium negative electrode from further reacting with the electrolyte, the naturally formed SEI film is not uniform and brittle, and lithium dendrites continuously growing on the surface of the lithium negative electrode during battery cycling can pierce the formed SEI film to allow the metallic lithium to directly contact and react with the electrolyte to form a new SEI film. Lithium dendrite generated due to uneven lithium deposition and dissolution can continuously puncture a new SEI film in cycles, so that the SEI film is continuously broken and repaired, the metal lithium negative electrode continuously reacts with electrolyte repeatedly, and meanwhile, the lithium dendrite on the surface of the lithium negative electrode continuously grows, and the performance of the battery is seriously influenced. Therefore, the problem of the lithium negative electrode is that the SEI layer with stable electrochemical performance and good mechanical performance is formed on the surface of the lithium metal, which is an effective and feasible method.
During the past decade, researchers have made much effort to obtain the ideal SEI layer. However, unlike the conventional graphite and silicon negative electrodes, the surface energy of lithium metal is low, so that the conventional coating and sputtering processes cannot obtain a stable SEI film on the surface of lithium, and for the lithium metal negative electrode, how to improve the bonding strength of the lithium metal and the SEI film is the key to whether the artificial SEI film can obtain a good effect.
Therefore, the invention provides an in-situ generation technology of an artificial SEI film, which utilizes the direct reaction of metallic lithium and acetic acid to form a lithium acetate SEI film on the surface of lithium metal in situ, the film is uniform and has strong bonding force with the surface of the metallic lithium, and the film cannot be broken in the using process of a battery, so that the cycle of forming, breaking and forming of the traditional SEI film is avoided, and a lithium cathode continuously reacts with an electrolyte to form dendrites and dead lithium; on the other hand, lithium acetate and the traditional electrolyte or solid electrolyte components are chemically inert and do not react with each other; in conclusion, the lithium acetate effectively improves the cycle performance of the lithium battery on the surface of lithium metal through the in-situ synthesis technology, and effectively solves the problem of weak binding force of an SEI film of the lithium metal battery.
Disclosure of Invention
In order to solve the problems that the conventional artificial SEI film technology cannot be completely bonded on the surface of lithium metal and is easy to fall off and break, the invention provides a modified lithium metal negative electrode battery which comprises a positive electrode, an electrolyte and a modified lithium metal negative electrode.
The modified metal lithium cathode is obtained by reacting a metal lithium cathode with acetic acid steam in the acetic acid steam.
According to the invention, acetic acid reacts with a lithium cathode to generate a layer of lithium acetate passivation film on the surface of lithium metal. The method mainly uses acetic acid steam to react with the metal lithium to form a lithium acetate passive film on the surface of the metal lithium, and the reaction degree and the film thickness can be controlled by controlling the reaction time. Wherein, the metallic lithium and acetic acid react as follows:
2Li+2CH3COOH→2CH3COOLi+H2
because the acetic acid directly reacts with lithium as a negative electrode material in situ, the lithium acetate passive film has stronger binding power with lithium metal and is not easy to fall off in the use process of the battery.
Preferably, the lithium metal cathode reacts with acetic acid vapor, and the chemical reaction with acetic acid is violent due to the active chemical property of lithium, so that if the lithium metal cathode reacts in a liquid phase, the reaction speed and the reaction progress are not easy to control, the relevant parameters of a finished product of the modified lithium metal cathode are not easy to regulate and control, and compared with the prior art, the gas phase reaction is mild, and the reaction process can be controlled through the process parameters such as the retention time.
The reaction of acetic acid vapor and lithium metal is carried out under the anhydrous and oxygen-free conditions, preferably under the normal temperature condition (25 ℃), the boiling point of acetic acid is 118 ℃, and the melting point of lithium simple substance is 180 ℃, so that the lithium metal has the risk of softening or even melting under the heating condition to influence the final performance of the product; meanwhile, in order to increase the volatilization speed of acetic acid at normal temperature, the reaction is preferably carried out under a negative pressure condition to prevent acetic acid vapor from liquefying at normal temperature; if necessary, inert gas can be introduced into the reaction vessel to adjust the reaction pressure and the partial pressure of the gaseous product hydrogen, so as to avoid the danger of explosion.
Preferably, the retention time is 1-30min, more preferably, the retention time is 1-15 min, most preferably, the retention time is 1-5min, under the condition of extremely short retention time, the acetic acid steam can react with the lithium metal to generate a compact and complete lithium acetate passive film, and compared with other SEI artificial synthesis technologies and other lithium battery cathodes coated with SEI films, the lithium ion battery cathode has higher industrial production efficiency and better effect.
As one mode, the reaction is carried out in an intermittent mode, after the reaction is finished, gas in the reaction container is pumped out through a fan, and separation of acetic acid steam and hydrogen/inert gas is realized through a condensation mode or an alkali liquor absorption mode.
The modified lithium metal negative electrode according to the present invention may be a lithium foil, or may be composed of a current collector and a negative electrode active material containing lithium metal;
the lithium foil may be lithium metal or a lithium alloy;
preferably, the lithium alloy may be one of an aluminum lithium alloy, a lithium tin alloy, a lithium lead alloy, and a lithium silicon alloy.
As an alternative to the negative electrode, the current collector and the negative electrode active material containing metallic lithium may be a conventional negative electrode in the related art; the current collector may be a copper foil, and the negative electrode active material may be lithium metal or a lithium alloy, and preferably, the lithium alloy may be one of an aluminum lithium alloy, a lithium tin alloy, a lithium lead alloy, and a lithium silicon alloy.
Preferably, the negative electrode active material may form an active material layer by combining with a binder, which may be one or more of polytetrafluoroethylene, styrene-butadiene rubber, hydroxypropylmethylcellulose, sodium carboxymethylcellulose, hydroxyethylcellulose, and polyvinyl alcohol. The amount of the binder may be used in the conventional amount thereof. The binder may be used in an amount of 2 to 50% by weight with respect to 100 parts by weight of the anode active material.
The positive electrode of the modified metal lithium negative electrode battery comprises a positive electrode current collector and a positive electrode active material;
the selection of the positive electrode current collector is not particularly limited, and preferably, the positive electrode current collector is an aluminum foil;
the selection of the positive electrode active material is not particularly limited, and preferably, the positive electrode active material is one or more of LiCoO2, LiMnO2, LiNiO2, LiVO2, LiNi1/3Co1/3Mn1/3O2, LiMn2O4, Li4Ti5O12, Li (ni0.5mn1.5) O4LiFePO4, LiMnPO4, LiNiPO4, and LiCoPO 4.
The modified lithium metal negative electrode battery can be applied to a non-aqueous electrolyte system lithium battery, preferably, the non-aqueous electrolyte comprises a lithium salt and a non-aqueous solvent, and the modified lithium metal negative electrode battery further comprises a diaphragm, wherein the diaphragm is positioned between a positive electrode and a negative electrode;
preferably, the non-aqueous solvent is one or more of Ethylene Carbonate (EC), Propylene Carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), ethyl carbonate, butylene carbonate, γ -butyrolactone, sulfolane, acetonitrile, 1, 2-dimethoxyethane, 1, 3-dimethoxypropane, diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran;
preferably, the lithium salt is one or more of LiPF6, LiBF4, LiClO4, LiAsF6, LiCF3SO3 and LiN (CF3SO2) 2;
particularly preferably, the nonaqueous electrolytic solution may further include other various additives such as a flame retardant additive, an overcharge protection additive, and the like, which are common knowledge in the art and will not be described herein.
The separator is disposed between the positive electrode and the negative electrode, and has an electrical insulating property and a liquid retaining property. The separator may be selected from various separators used in lithium ion batteries, such as one or more of polyolefin microporous membrane, polypropylene, polyethylene felt, glass fiber felt or ultrafine glass fiber paper. Such membranes are well known to those skilled in the art.
The preparation method of the non-aqueous electrolyte system lithium battery comprises the steps of preparing a positive electrode, a negative electrode and an electrolyte of the battery, winding and separating the positive electrode and the negative electrode through a diaphragm to form an electrode group, placing the electrode group into a battery shell, adding the electrolyte, and then sealing the battery shell, wherein the negative electrode is the negative electrode provided by the invention.
The modified metal lithium negative electrode battery can be applied to a solid electrolyte system, and the solid electrolyte material can be a crystalline material or an amorphous material. The solid electrolyte material may be glass or crystallized glass (glass ceramic). Examples of the shape of the solid electrolyte material include a particulate shape.
Preferably, the solid electrolyte is one of an oxide solid electrolyte, a sulfide solid electrolyte, and a polymer solid electrolyte.
The oxide solid electrolyte may be, for example, LiPON (lithium oxynitride phosphate), li1.3al0.3ti0.7(PO4)3, la0.51li0.34tio0.74, Li3PO4, Li2SiO2, Li2SiO4, or the like as an oxide solid electrolyte.
The polymer electrolyte used in the present invention generally contains a metal salt and a polymer. In the case where the metal battery according to the present invention is a lithium battery, a lithium salt may be used as the metal salt. As the lithium salt, at least any one of the above inorganic lithium salt and organic lithium salt may be used. The polymer is not particularly limited as long as it forms a complex with a lithium salt, and examples thereof include polyethylene oxide and the like.
Examples of the sulfide solid electrolyte include Li 2-P2S, Li 2-P2S-LiI, Li 2-P2S-Li 2-LiI, Li 2-SiS-LiI, Li 2-SiS-LiBr, Li 2-SiS-LiCl, Li 2-SiS-B2S-LiI, Li 2-SiS-P2S-LiI, Li 2-B2S, Li 2-P2S-ZmSn (where M and n are positive numbers and Z are any of Ge, Zn and Ga), Li 2-GeS, Li 2-SiS-Li 3PO and Li 2-SiS-LixMOy (where x and y are positive numbers and M is any of P, Si, Ge, B, Al, Ga and In). Note that the above description of "Li 2S — P2S 5" refers to a sulfide solid electrolyte material formed using a raw material composition containing Li2S and P2S5, and the same applies to other descriptions.
The sulfide solid electrolyte material may contain lithium halide in addition to the above-described ion conductor. Examples of the lithium halide include LiF, LiCl, LiBr, and LiI, and among them, LiCl, LiBr, and LiI are preferable. The ratio of LiX (X ═ F, I, Cl, Br) in the sulfide solid electrolyte material is, for example, in the range of 5 mol% to 30 mol%, and may be in the range of 15 mol% to 25 mol%.
Examples of the solid electrolyte used in the present invention include Li2Ti (PO4)3-AlPO4(Ohara glass) and the like in addition to the above.
The present invention preferably uses a solid electrolyte because of its advantages in solving lithium dendrites, avoiding short circuits, etc.
Another aspect of the present invention is to provide a method for preparing a modified lithium metal negative electrode battery, which includes the steps of:
1) preparing a positive electrode;
2) the lithium metal negative electrode is reacted with acetic acid to obtain a modified lithium metal negative electrode;
3) and (3) assembling the positive electrode obtained in the step 1) and the negative electrode obtained in the step 2) with an electrolyte to form a modified metal lithium negative electrode battery.
Preferably, the lithium metal cathode reacts with acetic acid vapor, and the chemical reaction with acetic acid is violent due to the active chemical property of lithium, so that if the lithium metal cathode reacts in a liquid phase, the reaction speed and the reaction progress are not easy to control, the relevant parameters of a finished product of the modified lithium metal cathode are not easy to regulate and control, and compared with the prior art, the gas phase reaction is mild, and the reaction process can be controlled through the process parameters such as the retention time.
Due to the active chemical property of metal lithium, preferably, the reaction of acetic acid vapor and lithium metal is carried out under the anhydrous and oxygen-free conditions, preferably under the normal temperature condition (25 ℃), the boiling point of acetic acid is 118 ℃, the melting point of lithium simple substance is 180 ℃, therefore, the lithium metal has the risk of softening or even melting under the heating condition to influence the final performance of the product; meanwhile, in order to increase the volatilization speed of acetic acid at normal temperature, the reaction is preferably carried out under a negative pressure condition to prevent acetic acid vapor from liquefying at normal temperature; if necessary, inert gas can be introduced into the reaction vessel to adjust the reaction pressure and the partial pressure of the gaseous product hydrogen, so as to avoid the danger of explosion.
Preferably, the retention time is 1-30min, more preferably, the retention time is 1-15 min, most preferably, the retention time is 1-5min, under the condition of extremely short retention time, the acetic acid steam can react with the lithium metal to generate a compact and complete lithium acetate passive film, and compared with other SEI artificial synthesis technologies and other lithium battery cathodes coated with SEI films, the lithium ion battery cathode has higher industrial production efficiency and better effect.
As one mode, the reaction is carried out in an intermittent mode, after the reaction is finished, gas in the reaction container is pumped out through a fan, and separation of acetic acid steam and hydrogen/inert gas is realized through a condensation mode or an alkali liquor absorption mode.
The method for producing the positive electrode according to the present invention can be produced by a method which is conventional in the art, for example, by dissolving a positive electrode active material, a conductive material, and a binder in an organic solvent, and then coating and drying the same on a positive electrode current collector.
The negative electrode according to the present invention can be obtained in the same manner as the positive electrode, for example, by dissolving a negative electrode active material and a binder in a solvent, coating the solution on a negative electrode current collector, and drying the coating; a lithium foil or a lithium alloy foil may be used as it is as the negative electrode.
The selection of the materials for the positive and negative electrodes is described above and will not be described in detail here.
The invention also provides a lithium metal negative electrode, which comprises a negative electrode active material and a passivation film covering the surface of the negative electrode active material, wherein the passivation film contains lithium acetate.
Preferably, the thickness of the passivation film is 10 nm to 1000 μm, preferably 100 nm to 100 μm, preferably 100 nm to 1 μm.
The thickness of the passivation film can be obtained by adjusting the reaction time of acetic acid and lithium and the concentration of acetic acid. For liquid phase reaction, the concentration of acetic acid solution can be adjusted, the acetic acid solution can be organic solution of acetic acid, such as ethanol solution of acetic acid, and preferably, the mass fraction of acetic acid is 5-30%; for gas phase reactions, this can be achieved by adjusting the partial pressure of acetic acid vapor.
Preferably, the negative active material may be lithium metal or a lithium alloy, and preferably, the lithium alloy may be one of an aluminum lithium alloy, a lithium tin alloy, a lithium lead alloy, and a lithium silicon alloy.
As one application of the metallic lithium negative electrode, a lithium air battery, a lithium sulfur battery, a lithium ion battery may be mentioned.
The negative electrode related to the lithium-sulfur battery is the metal lithium battery, the positive active substance of the metal lithium battery is a sulfur-carbon composite material, and the electrolyte and the diaphragm are respectively conventional electrolyte and diaphragm of the lithium-sulfur battery, and detailed description is omitted here.
The sulfur-carbon composite is prepared by mixing sulfur steam and a conductive additive, wherein the mass ratio of the sulfur steam to the conductive additive can be adjusted according to actual use requirements, and the sulfur steam and the conductive additive are heated at the temperature of 160 ℃ below 145 ℃ after being mixed to obtain the sulfur-carbon composite. The conductive additive can be carbon black materials such as acetylene black, SuperP, SuperS, 350G, carbon fiber (VGCF), Carbon Nanotubes (CNTs), Ketjen black and the like.
In the lithium-air battery, the related negative electrode is the lithium metal negative electrode, the positive active material is oxygen, and the related electrolyte and the related diaphragm are the electrolyte and the diaphragm commonly used for the lithium-air battery, and detailed description thereof is omitted.
Effects of the invention
The CH3COOLi-Li cathode is obtained by generating lithium acetate on the surface of lithium metal in situ, a lithium acetate passive film formed on the surface of the CH3COOLi-Li cathode can inhibit the reaction of lithium dendrites and inhibit the growth of the lithium dendrites in the circulation process, and because the lithium acetate is synthesized in situ, the binding force between the passive film and the lithium metal is enhanced, the circulation performance of the battery is greatly improved, the problem of weak binding force of a lithium metal SEI film is solved, and the obtained metal lithium cathode has better performance in lithium ion batteries, lithium sulfur batteries and lithium air batteries.
Drawings
FIG. 1 lithium cobaltate all-cell cycle performance for CH3COOLi-Li cathode and pure Li cathode
FIG. 2 shows the charge and discharge curves of the full lithium cobaltate batteries corresponding to the CH3COOLi-Li cathode and the pure Li cathode with the processing time of 1min at the 2 nd circle and the 300 th circle
FIG. 3 shows the cycle performance of a lithium cobaltate full cell assembled by a CH3COOLi-Li cathode with a treatment time of 1min
FIG. 4 SEM image of lithium plate surface after acetic acid gas reaction for 1min
FIG. 5 XRD pattern of lithium plate surface after acetic acid gas reaction for 1min
FIG. 6 is a graph of the test results of a CH3COOLi-Li cathode assembled lithium copper battery at different processing times;
FIG. 7 shows the charge and discharge curves of the lithium copper battery at the 100 th cycle;
FIG. 8 is a charge-discharge curve of different cycles of the CH3COOLi-Li negative electrode cycle with a processing time of 1 min;
FIG. 9 charging and discharging curves of different cycles of pureLi negative electrode cycle
Fig. 10 SEM image of 80 cycles of negative electrode material for lithium copper battery: wherein (a) pureLi cathode is 20000 times; (b) pureLi cathode, 80000 times; (c) 20000 times of CH3COOLi-Li cathode; (d) 80000 times of CH3COOLi-Li cathode;
fig. 11 is a graph of the cycle test results for a lithium battery assembled from a CH3COOLi-Li negative electrode and a pureLi negative electrode, with charge and discharge current densities: 1mAcm-2
Fig. 12 is a graph of the cycle test results for a lithium battery assembled from a CH3COOLi-Li negative electrode and a pureLi negative electrode, with charge and discharge current densities: 3mAcm-2
Detailed Description
Example 1
1.1 preparation of CH3COOLi-Li cathode
And (3) putting the lithium sheet into acetic acid steam under the conditions of no water, no oxygen, negative pressure and normal temperature, and staying for 1min to generate a lithium acetate passivation film on the surface of the lithium sheet to obtain the CH3COOLi-Li cathode. As shown in FIG. 1, FIG. 1 is an SEM image of the surface of a lithium plate after the acetic acid vapor reaction for 1 min. It can be seen that the lithium acetate passive film generated by the reaction on the surface of the lithium sheet is blocky and has a relatively flat surface.
1.2 preparation of the Positive electrode
According to the mass ratio of 90: 5: and 5, taking lithium cobaltate, PVDF and acetylene black according to the proportion, sequentially adding the lithium cobaltate, the PVDF and the acetylene black into an NMP solvent (the ratio of the PVDF to the NMP is 1:35), magnetically stirring for 12 hours to obtain uniformly dispersed lithium cobaltate slurry, coating the lithium cobaltate slurry on an aluminum foil, putting the aluminum foil into a vacuum oven for baking for 12 hours at the temperature of 80 ℃, and punching the obtained sample according to the required size to obtain the lithium cobaltate positive plate.
1.3 lithium Battery Assembly
A CH3COOLi-Li and lithium cobaltate positive plate negative electrode is used for assembling a CH3COOLi-Li ║ LiCoO2 battery, 1MLiPF6 ║ EC/DMC (1: 1) is adopted as an electrolyte, Celgard2325 is adopted as a diaphragm, and constant-current charge and discharge tests are carried out, wherein the charge and discharge multiplying power is 0.5C.
Example 2
An oxide solid electrolyte was used instead of the electrolytic solution, and other elements were the same as in example 1, and the oxide solid electrolyte was li1.3al0.3ti0.7(PO4) 3.
Example 3
A CH3COOLi-Li ║ Cu battery is assembled by using the CH3COOLi-Li cathode and the copper sheet prepared in the step 1.1 in the example 1, 1MLiTFSI ║ DME/DOL (1: 1) is adopted as an electrolyte, Celgard2325 is adopted as a diaphragm, a constant-current charge-discharge test is carried out, the discharge time is 1 hour, the charge-discharge current density is 1mAcm-2, and the capacity density is 1 mAhcm-2.
Example 4
The residence time was 3min, and the rest was the same as in example 1.
Example 5
The residence time was 5min, and the rest was the same as in example 1.
Example 6
The residence time was 30min, and the rest was the same as in example 1.
Example 7
The residence time was 3min, and the rest was the same as in example 3.
Example 8
The residence time was 5min, and the rest was the same as in example 3.
Example 9
The residence time was 30min, and the rest was the same as in example 3.
Example 10
CH3COOLi-Li ║ CH3COOLi-Li and Li ║ Li symmetrical batteries were assembled with the CH3COOLi-Li negative electrode and the Li negative electrode prepared in example 1, respectively, a constant current charge and discharge test was performed with an electrolyte of 1M LiPF6 ║ EC/DMC (1: 1) and a separator of Celgard2325 for 2 hours, and the batteries were charged and discharged with current densities of two magnitudes, 1mAcm-2 and 3mAcm-2, and the capacity density was 1 mAcm-2.
Comparative example 1
The same procedure as in example 1 was repeated except that a lithium plate was used instead of the CH3COOLi-Li negative electrode.
Comparative example 2
And dissolving 3g of lithium acetate solution in 30ml of ethanol solution to prepare a lithium acetate solution with the mass concentration of 10%, coating the lithium acetate solution on a lithium foil, and drying to obtain the lithium acetate negative plate. The resulting lithium acetate negative plate was assembled into a CH3COOLi-Li ║ LiCoO2 battery cell as in example 1, step 1.3.
Comparative example 3
The same procedure as in example 3 was repeated except that a lithium plate was used instead of the CH3COOLi-Li negative electrode.
Comparative example 4
The same procedure as in example 10 was repeated except that a lithium plate was used instead of the CH3COOLi-Li negative electrode.
The first discharge capacity of the lithium cobaltate battery assembled by the pure Li negative electrode is 128.24mAh/g, the first discharge capacity of the lithium cobaltate battery assembled by the CH3COOLi-Li negative electrode in the embodiment 1 is 128.99mAh/g, and the difference is small, which shows that the lithium acetate passive film generated by the in-situ reaction has little influence on the deposition and dissolution of lithium ions. At the beginning of 320 cycles, the battery capacity of the pure Li negative electrode began to jump water, indicating that the lithium dendrites that continuously grow during the cycling process have reached a level that severely hampered the battery charge-discharge cycling; the CH3COOLi-Li cathode prepared in the embodiment 1 does not have the phenomenon of sudden battery capacity drop, and the cycle is stable. For different in-situ reaction times, after 500 cycles, the specific discharge capacity of the battery using the CH3COOLi-Li cathode of example 1 is 112.21mAh/g, and the capacity retention rate is 87.0%.
The charge and discharge performance of the CH3COOLi-Li negative electrode in example 1, the CH3COOLi-Li negative electrode in comparative example 2 and the pure Li negative electrode in circle 2 shows no obvious difference in charge capacity, discharge capacity and discharge average voltage. After 300 cycles, the specific discharge capacity of the battery using the pure Li cathode is 94.92mAh/g, the capacity retention rate is only 74.0%, the specific discharge capacity of the CH3COOLi-Li cathode of the comparative example 2 is 105.88mAh/g, the capacity retention rate is 82.7%, the battery using the CH3COOLi-Li cathode with the reaction time of 1min has the capacity of 116.63mAh/g, and the capacity retention rate is 90.4%. This shows that the cycle performance of the CH3COOLi-Li negative electrode after treatment is significantly improved. The reason is that the lithium acetate passive film on the surface greatly slows down the reaction between the Li negative electrode and the electrolyte, and the charge-discharge current on the surface of the lithium negative electrode is uniform, so that the growth of lithium dendrite is inhibited. The discharge specific capacity of the CH3COOLi-Li cathode in 1000 cycles of the embodiment 1 is 94.79mAh/g, the capacity retention rate is still 73.5%, and the coulombic efficiency is stabilized above 98%, so that the excellent cycle stability of the CH3COOLi-Li cathode is reflected, and compared with the traditional ex-situ coating technology, the passive film obtained by in-situ synthesis has longer action time and more obvious performance improvement on the battery.
Fig. 1 shows full battery cycle performance diagrams of CH3COOLi-Li cathodes and pure Li cathodes obtained by in-situ reactions at different times (examples 1 and 4 to 6), wherein the first discharge capacity of a lithium cobalt oxide battery assembled by a pure Li cathode is 128.24mAh/g, the first discharge capacity of a lithium cobalt oxide battery assembled by a CH3COOLi-Li cathode of example 1 is 128.99mAh/g, and the difference is small, which indicates that a lithium acetate passivation film generated by the in-situ reactions has little influence on deposition and dissolution of lithium ions. At the beginning of 320 cycles, the battery capacity of the pure Li negative electrode began to jump water, indicating that the lithium dendrites that continuously grow during the cycling process have reached a level that severely hampered the battery charge-discharge cycling; and the CH3COOLi-Li cathode obtained by the in-situ reaction does not have the phenomenon of sudden battery capacity drop, and the cycle is stable. For different in-situ reaction times, after 500 cycles, the battery discharge specific capacity of the CH3COOLi-Li cathode in the embodiment 1 is 112.21mAh/g, and the capacity retention rate is 87.0%; the battery capacity of the CH3COOLi-Li cathode of the embodiment 4 is 96.68mAh/g, and the capacity-discharge ratio retention rate is 74.6%; the specific discharge capacity of the CH3COOLi-Li negative electrode in example 5 was 74.03mAh/g, and the capacity retention rate was 54.8%. The discharge specific capacity of the battery with the CH3COOLi-Li cathode in the embodiment 6 is only 41.84mAh/g after 200 cycles, and the capacity retention rate is only 34.5%. It can be seen that as the reaction time increases, the capacity performance of the corresponding battery decreases and the cycle stability performance decreases, which may be due to the fact that the reaction time increases to cause a thicker passivation film to be formed on the surface of the lithium metal, which affects the transfer of lithium ions and electrons, thereby affecting the battery performance. Where the rapid decrease in the capacity of the CH3COOLi-Li negative electrode of example 6 indicates that the passivation film formed under this condition is thick and has severely impeded cycling of the cell. Therefore, the CH3COOLi-Li negative electrode of the embodiment 1 has the best modification effect and better electrochemical performance.
The lithium copper battery is mainly used for exploring the deposition and dissolution processes of lithium and characterizing the coulombic efficiency and the cycling stability of a negative electrode material. Fig. 6 is a graph of the cycling efficiency of the cell corresponding to the CH3COOLi-Li cathode and the pure Li cathode obtained at different reaction times. As can be seen from the figure, the coulombic efficiency of the CH3COOLi — Li negative electrodes of examples 3 and 7 is not attenuated after 100 cycles of cycling, and is stabilized at about 97%, and the cycling stability performance is superior to that of other sample groups. The negative electrode coulombic efficiency of example 8 started to decay at 100 cycles, but was still improved compared to the pure Li negative electrode. The coulombic efficiency of the pure Li negative electrode is rapidly reduced when the pure Li negative electrode circulates for 70 circles, the coulombic efficiency is reduced to be below 80% when the pure Li negative electrode circulates for 77 circles, probably because dendritic crystals of the metal lithium negative electrode continuously grow after long-time circulation, lithium deposited on the surface of the pure Li negative electrode gradually becomes loose dead Li, the dissolution and deposition of the lithium are hindered, the performance of the battery is seriously influenced, the direct contact of the metal lithium and electrolyte is prevented due to the fact that a lithium acetate passivation film exists on the surface of the CH3COOLi-Li negative electrode, the surface current of the metal lithium negative electrode is uniform in the charging and discharging process, the generation of lithium dendritic crystals is inhibited to a certain extent, and therefore the circulation stability of the pure Li negative electrode is improved. In example 9, the coulombic efficiency is obviously reduced, which is probably because the reaction time is too long, and the generated lithium acetate passivation film is thick, thereby blocking the transmission of lithium ions and electrons and influencing the electrochemical performance of the corresponding battery.
The polarization voltage of the lithium copper battery is the difference voltage of a charging and discharging platform, and the smaller the polarization voltage is, the more stable the battery is in the process of depositing and dissolving lithium. Fig. 7 shows the charge-discharge curves at cycle 100 for CH3COOLi-Li cathodes and pure Li cathodes at different reaction times, and it can also be seen that the samples of examples 3 and 7 have higher coulombic efficiencies, while the CH3COOLi-Li cathodes have lower polarization voltages compared to the pure Li cathodes. The polarization voltage of a pure Li cathode is about 78mV when the pure Li cathode is cycled for 100 circles, the polarization voltage of a CH3COOLi-Li cathode is about 50mV when the pure Li cathode is cycled for 100 circles, and the cathode is more stable when the processed sample has a lower polarization voltage when the pure Li cathode is cycled for 100 circles. Fig. 8 and 9 show charge and discharge curves of the CH3COOLi-Li negative electrode and the pure Li negative electrode of example 3 at the 10 th, 20 th, 60 th and 80 th turns, respectively. The CH3COOLi-Li cathode has a complex process of forming an SEI film during the first ten cycles, so that the polarization voltage is higher at the beginning and continuously becomes smaller and tends to be stable in the subsequent cycles, and the polarization voltage of the CH3COOLi-Li cathode is approximately stabilized at about 50mV after 80 cycles of cycling, thereby showing the good stability of the CH3COOLi-Li cathode. And the pure Li cathode has the polarization voltage of 53mV at the cycle of 60, the polarization voltage is increased to 69mV at the cycle of 80, and the increase of the polarization voltage corresponds to the phenomenon that the coulombic efficiency begins to decrease at the cycle of 60, which represents the instability of the pure Li cathode, and the lithium dendrite on the surface of the lithium cathode at the cycle of 80 can seriously obstruct the deposition and dissolution process of lithium.
In order to further explore the reason of the coulomb efficiency attenuation of the lithium negative electrode, the lithium copper battery which is cycled for 80 circles is disassembled, and the cycled lithium negative electrode is subjected to SEM test. Fig. 10 gives SEM images of the lithium copper battery of CH3COOLi-Li negative electrode and pureLi negative electrode at cycle 80 cycles of the lithium negative electrode, where fig. 10a and 10b are pureLi negative electrodes, fig. 10c and 10d are CH3COOLi-Li negative electrodes, magnification 20000 times and 80000 times, respectively. It can be seen that after 80 cycles, a layer of rod-shaped dead lithium grows on the surface of the pureLi negative electrode, and the dead lithium is attached to the surface of a lithium sheet to prevent further deposition and dissolution of lithium, so that the coulombic efficiency of the battery is low, and the battery is dead. In contrast, the surface of the CH3COOLi-Li cathode is deposited with granular lithium, and the surface is smooth without obvious lithium dendrites and dead lithium.
The charge and discharge test is carried out by assembling CH3COOLi-Li ║ CH3COOLi-Li and Li ║ Li symmetrical batteries, a sample group with the reaction time of 1min is selected for a CH3COOLi-Li cathode, the polarization voltage of a pure Li cathode begins to gradually increase from 200h to about 330h, the polarization voltage is steeply increased, the polarization voltage is increased due to the continuous growth of lithium dendrites, the sudden increase of the polarization voltage occurs in 330h, which indicates that the lithium dendrites seriously affect the cycle performance of the lithium battery at the moment, and the polarization voltage of 378h is reduced to 38mV because the lithium dendrites puncture a diaphragm to cause the short circuit of the battery. Compared with the prior art, the CH3COOLi-Li cathode has smaller and more stable polarization voltage in the circulation process, the polarization voltage is slowly increased in 400 hours of circulation, and the polarization voltage is only 70mV in 350 hours of circulation, which shows that the lithium acetate passive film can prevent the growth of lithium dendrites and improve the circulation stability of the lithium cathode. The polarization voltage of the CH3COOLi-Li cathode and the pure Li cathode is larger, the polarization voltage of the pure Li cathode starts to increase after 90h of circulation, and the polarization voltage of the CH3COOLi-Li cathode is more stable in the circulation process. It can be seen that the CH3COOLi-Li cathode exhibits better stability during high rate cycling, which is closely related to the protection of the lithium acetate passivation film, the passivation layer avoids side reactions of the lithium cathode with the electrolyte, and at the same time, the current on the surface of the lithium cathode can be homogenized during cycling.
The impedance of the battery is in a trend of firstly reducing and then increasing, the gradual reduction of the impedance at the beginning of circulation can be interpreted as that the battery has a process that the electrolyte soaks the anode and the cathode, and then the impedance is increased because the lithium dendrites are continuously increased to influence the transmission of lithium ions. The impedance of the pure Li cathode is stabilized at 110 omega 50h before circulation, the impedance of the CH3COOLi-Li cathode is only 60 omega, and the impedance of the CH3COOLi-Li cathode is smaller than that of the pure Li cathode in the coming circulation stabilization. The impedance of the pure Li cathode starts to increase in the following cycle, which has already increased to 250 Ω up to 300h, while the impedance of the CH3COOLi-Li cathode increases slowly and only has 99 Ω up to 300 h. The result corresponds to the battery cycle data, and the impedance change of the CH3COOLi-Li cathode in the long cycle process is small, so that the stability is better.
Claims (6)
1. A modified metal lithium negative electrode battery comprises a positive electrode, an electrolyte and a modified metal lithium negative electrode, and is characterized in that the modified metal lithium negative electrode is obtained by reacting the metal lithium negative electrode with acetic acid;
the metallic lithium negative electrode is one of metallic lithium alloys;
the lithium alloy is one of lithium aluminum alloy, lithium tin alloy, lithium lead alloy and lithium silicon alloy;
the modified metal lithium cathode is obtained by reacting a metal lithium cathode with acetic acid steam in the acetic acid steam;
the steam reaction is carried out under the condition of negative pressure;
the steam reaction is carried out at normal temperature;
the steam reaction residence time is 1-5 min.
2. The modified lithium metal anode battery of claim 1, wherein the electrolyte is a non-aqueous electrolyte;
the non-aqueous electrolyte comprises a lithium salt and a non-aqueous solvent, and the modified lithium metal negative electrode battery further comprises a diaphragm; the non-aqueous solvent is one or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, butylene carbonate, gamma-butyrolactone, sulfolane, acetonitrile, 1, 2-dimethoxyethane, 1, 3-dimethoxypropane, diethyl ether, tetrahydrofuran and 2-methyltetrahydrofuran;
the lithium salt is LiPF6、LiBF4、LiClO4、LiAsF6、LiCF3SO3、LiN(CF3SO2)2One or more of them.
3. The modified lithium metal anode battery of claim 1, wherein the electrolyte is a solid state electrolyte;
the solid electrolyte is one of an oxide solid electrolyte, a sulfide solid electrolyte and a polymer solid electrolyte.
4. The modified lithium metal anode battery of claim 1, wherein the electrolyte is a gel electrolyte.
5. The modified metallic lithium negative electrode battery of claim 1, wherein the positive electrode comprises a current collector and a positive electrode active material;
the positive electrode current collector is an aluminum foil;
the positive electrode active material is LiCoO2、LiMnO2、LiNiO2、LiVO2、LiNi1/3Co1/3Mn1/3O2、LiMn2O4、Li4Ti5O12、Li(Ni0.5Mn1.5)O4、LiFePO4、LiMnPO4、LiNiPO4、LiCoPO4One or more of them.
6. A method of making a modified metallic lithium negative electrode battery as claimed in any one of claims 1 to 5, comprising the steps of:
1) preparing a positive electrode;
2) the metal lithium negative electrode is reacted with acetic acid steam under the anhydrous and oxygen-free conditions to obtain a modified metal lithium negative electrode;
3) and (3) assembling the positive electrode obtained in the step 1) and the negative electrode obtained in the step 2) with an electrolyte to form a modified metal lithium negative electrode battery.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005089352A2 (en) * | 2004-03-16 | 2005-09-29 | Toyota Technical Canter Usa, Inc. | Battery with molten salt electrolyte and protected lithium-based negative electrode material |
| CN107359310A (en) * | 2017-07-07 | 2017-11-17 | 北京理工大学 | The method of modifying and modified metal lithium titanate cathode material of lithium secondary battery lithium anode material |
| CN109244370A (en) * | 2018-10-23 | 2019-01-18 | 北京航空航天大学 | A kind of preparation method of secondary lithium metal cathode steam protection film |
| CN110518226A (en) * | 2019-09-10 | 2019-11-29 | 石家庄尚太科技有限公司 | A kind of silicon-carbon composite cathode material and preparation method thereof |
| CN110931711A (en) * | 2018-09-19 | 2020-03-27 | 国家能源投资集团有限责任公司 | Lithium metal negative electrode, preparation method thereof and lithium metal battery |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7247408B2 (en) * | 1999-11-23 | 2007-07-24 | Sion Power Corporation | Lithium anodes for electrochemical cells |
| CN104022275B (en) * | 2014-05-28 | 2016-04-27 | 上海纳米技术及应用国家工程研究中心有限公司 | Freeze drying micro emulsion legal system is ready for use on the lithium titanate material of lithium cell negative pole |
| KR102148507B1 (en) * | 2017-07-26 | 2020-08-26 | 주식회사 엘지화학 | Lithium Metal Electrode and Method for Preparing the Same |
| CN108376763A (en) * | 2018-02-05 | 2018-08-07 | 电子科技大学 | A kind of composite negative pole structure, solid lithium battery battery core, solid lithium battery and preparation method thereof |
| WO2019156005A1 (en) * | 2018-02-07 | 2019-08-15 | 株式会社アルバック | Thin film formation method, thin film formation device, and lithium battery |
| CN110429281A (en) * | 2019-08-01 | 2019-11-08 | 浙江锋锂新能源科技有限公司 | A kind of high-energy density all-solid-state battery based on sulfide solid electrolyte |
| CN110783551A (en) * | 2019-11-13 | 2020-02-11 | 华南师范大学 | Lithium electrode material, preparation method thereof and battery containing lithium electrode material |
-
2020
- 2020-02-28 CN CN202010126005.4A patent/CN111293299B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005089352A2 (en) * | 2004-03-16 | 2005-09-29 | Toyota Technical Canter Usa, Inc. | Battery with molten salt electrolyte and protected lithium-based negative electrode material |
| CN107359310A (en) * | 2017-07-07 | 2017-11-17 | 北京理工大学 | The method of modifying and modified metal lithium titanate cathode material of lithium secondary battery lithium anode material |
| CN110931711A (en) * | 2018-09-19 | 2020-03-27 | 国家能源投资集团有限责任公司 | Lithium metal negative electrode, preparation method thereof and lithium metal battery |
| CN109244370A (en) * | 2018-10-23 | 2019-01-18 | 北京航空航天大学 | A kind of preparation method of secondary lithium metal cathode steam protection film |
| CN110518226A (en) * | 2019-09-10 | 2019-11-29 | 石家庄尚太科技有限公司 | A kind of silicon-carbon composite cathode material and preparation method thereof |
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