CN113948693A - Lithium indium alloy cathode material for lithium battery and preparation method thereof - Google Patents
Lithium indium alloy cathode material for lithium battery and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of lithium battery cathode materials, and discloses a lithium indium alloy cathode material for a lithium battery and a preparation method thereof; in the lithium-indium alloy cathode material, the molar ratio of indium to lithium is 0.10-1, and the intermediate phase comprises Li13In3、Li3In、Li2In、Li3In2And Li5In4One or more of (a). When the lithium indium alloy cathode material is used as a lithium battery cathode, the first coulombic efficiency and the cycling stability of a lithium-manganese-rich cathode material can be improved, the discharge specific capacity of a lithium-sulfur battery can be improved, and the stability of the battery can be improved; in the preparation method of the invention, the mechanical alloying is used forCompared with the traditional alloy preparation method, the method has the advantages of simple and efficient process, no need of large-scale complex equipment and capability of reducing cost.
Description
Technical Field
The invention belongs to the technical field of lithium battery cathode materials, and particularly relates to a lithium indium alloy cathode material for a lithium battery and a preparation method thereof.
Background
With the development of science and technology, portable electronic products, electric vehicles and large-scale energy storage markets are rapidly developed, and the demands of people on secondary batteries with high energy density, cleanness, environmental protection and low cost are more and more urgent. The current commercial batteries include lead-acid batteries, zinc-manganese dry batteries, lithium batteries and the like, and the existing batteries have some defects, such as low energy density, harm to the environment, high cost and the like.
Lithium metal anodes have a very high theoretical capacity (3860mAh/g) and the lowest redox potential, and are considered to be the most promising anodes for rechargeable batteries. The carbon negative electrode (natural graphite, disordered carbon), silicon negative electrode, pure lithium negative electrode and the like exist as the negative electrode materials commercialized at the present stage and the negative electrode materials of the lithium battery researched, but the materials have defects and technical problems which are difficult to solve. Specifically, although carbon negative electrodes have the advantages of low cost, abundant resources, stable electrochemistry and the like and become the main commercialized negative electrode materials, the low capacity is the most important disadvantage; although the silicon negative electrode material has the advantages of abundant resources and high specific capacity, the volume expansion of the silicon negative electrode reaches 400% in the charging process, so that negative electrode particles are pulverized, and the cycle life is greatly shortened; although the pure lithium metal negative electrode has higher specific capacity and specific energy, the problems of uncontrolled growth of lithium dendrites, continuous change of volume, unstable solid electrolyte intermediate film and the like exist in the charging and discharging process, so that the cycle life of the lithium battery is poor, the coulombic efficiency is low, and serious potential safety hazards exist, and therefore, the finding of a high-efficiency, safe and long-life lithium battery negative electrode is very important.
The lithium alloy negative electrode not only has the advantages of high specific capacity and high specific energy of lithium metal, but also can inhibit the growth of lithium dendrite so as to improve the service life and the safety of the battery. However, most of the currently common lithium alloys are lithium aluminum, lithium tin alloys, etc., and the synthesis methods of these alloys are complex, which increases the cost.
Disclosure of Invention
The invention aims to provide a lithium indium alloy negative electrode material for a lithium battery, a preparation method thereof and the lithium battery, so as to solve one or more technical problems. When the lithium indium alloy cathode material is used as a lithium battery cathode, the first coulombic efficiency and the cycling stability of a lithium-manganese-rich cathode material can be improved, the discharge specific capacity of a lithium-sulfur battery can be improved, and the stability of the battery can be improved; the preparation principle of the invention is based on the mechanical alloying effect, and compared with the traditional alloy preparation method, the preparation method has the advantages of simple and efficient process, no need of large-scale complex equipment and capability of reducing the cost.
In order to achieve the purpose, the invention adopts the following technical scheme:
the lithium indium alloy negative electrode material for the lithium battery, disclosed by the invention, has the advantages that the molar ratio of indium to lithium is 0.10-1, and the intermediate phase comprises Li13In3、Li3In、Li2In、Li3In2And Li5In4One or more of (a).
A further improvement of the invention is that the mesophase serves as an active site for lithium deposition.
The further improvement of the invention is that in the lithium indium alloy cathode material, the intermediate phase forms a three-dimensional interconnected metal network structure.
The invention discloses a preparation method of a lithium indium alloy cathode material for a lithium battery, which comprises the following steps:
obtaining indium foil and lithium foil with preset thicknesses;
compounding the obtained lithium foil and indium foil to form a laminated structure, and performing rolling-folding-rolling repeatedly in a preset pressure range until the preset required thickness is reached to obtain a lithium indium alloy cathode material for a lithium battery;
the molar ratio of indium to lithium in the obtained lithium-indium alloy cathode material for the lithium battery is 0.10-1; the rolling-folding-rolling is carried out within a preset pressure range and is used for forming Li13In3、Li3In、Li2In、Li3In2And Li5In4One or more ofAn intermediate phase.
The invention is further improved in that the step of obtaining indium foil and lithium foil with preset thicknesses specifically comprises the following steps:
under the working condition that the water oxygen content meets the preset requirement, heating and melting indium, and scraping a surface oxide layer to obtain molten indium; casting the molten indium into a cooling device, cooling to room temperature, performing mechanical rolling until the thickness is 100-1000 microns, and obtaining indium foil with a preset thickness;
melting the lithium foil and removing the oxide layer to obtain molten lithium; and casting the molten lithium into a cooling device, cooling to room temperature, performing mechanical rolling until the thickness is 100-1000 microns, and obtaining the lithium foil with the preset thickness.
The invention is further improved in that the preset pressure range is 30-50 MPa.
The further improvement of the invention is that the rolling-folding-rolling is carried out under the preset pressure range, so that the intermediate phase forms a three-dimensional interconnected metal network structure.
According to the lithium battery, the negative electrode of the lithium battery adopts any one of the lithium-indium alloy negative electrode materials; or the lithium indium alloy cathode material prepared by the preparation method provided by the invention.
Compared with the prior art, the invention has the following beneficial effects:
in the alloy product, the indium element is introduced into the lithium metal to form an alloy, so that the oxidation tendency of pure lithium metal can be reduced; in the process of rolling lithium indium, the molar ratio of indium to lithium is 0.10-1, too much alloy phase causes too little flexibility of the rolled alloy texture when the ratio is too high, and the alloy phase is reduced when the ratio is too low, so that the effect of slowing dendritic crystal growth of the alloy is weakened.
By combining with the further explanation of the specific embodiment, the lithium indium alloy cathode material provided by the invention has the advantages that the first-circle discharge specific capacity can reach 299.35mAh/g, the charge-discharge coulombic efficiency can reach 86.7%, and the capacity retention rate can reach 82% after 150 cycles in a lithium-rich manganese-based cathode battery system at a current density of 0.1C. Under the current density of 0.2C in a lithium-sulfur battery system, the capacity retention rate can reach 88% after 100 cycles of circulation, and the attenuation rate relative to the first cycle can reach 0.1%.
According to the preparation method, the lithium indium alloy is formed through mechanical rolling treatment, and the lithium indium alloy can provide a three-dimensional interconnected metal network and provide a channel for transmission of lithium ions; the intermediate phase compound formed by rolling has strong affinity with metallic lithium, can be used as an active site for lithium deposition, keeps the structure unchanged, and has very high diffusion speed of the metallic lithium at the interface of the alloy phase. In addition, the lithium indium alloy foil pole piece prepared by laminating and rolling improves the problems of lithium dendrite growth, volume change and unstable solid electrolyte intermediate film in the battery cycle process of the pure lithium cathode, and compared with the traditional alloy preparation method, the improved method has simple and efficient process, does not need large-scale complex equipment, can reduce the cost, and has the possibility of realizing industrialization.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art are briefly introduced below; it is obvious that the drawings in the following description are some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is a lithium indium alloy phase diagram of a lithium indium alloy negative electrode prepared according to an example of the present invention;
FIG. 2 is a schematic diagram of a lithium indium alloy negative electrode material prepared in example 1 of the present invention; wherein, fig. 2(a) is a scanning photograph, and fig. 2(b) is an element distribution diagram;
fig. 3 is a schematic diagram showing comparison of first charge and discharge curves at 0.1C when a battery is assembled by matching the lithium-indium alloy negative electrode material prepared in example 2 of the present invention with a lithium-rich manganese-based positive electrode material;
fig. 4 is a schematic diagram showing the comparison of the cycle performance of 0.5C (voltage window of 2.0-4.8V) after the lithium-indium alloy cathode material prepared in embodiment 3 of the invention is assembled into a battery by matching with a lithium-rich manganese-based cathode material and activated for two cycles at 0.1C;
FIG. 5 is a schematic diagram illustrating a comparison of first charge-discharge curves of the lithium-indium alloy negative electrode material prepared in example 4 of the present invention at 0.05C in a lithium-sulfur battery system;
FIG. 6 is a schematic diagram showing the comparison of the cycle performance at 0.2C (voltage window is 1.7-2.8V) of the lithium-indium alloy cathode material prepared in example 5 after two cycles of activation at 0.05C and 0.1C;
FIG. 7 is a graph showing the comparison of the oxidation resistance of the lithium indium alloy negative electrode material prepared in example 6 of the present invention and a pure lithium negative electrode after being placed in the air for five minutes; fig. 7(a) is a schematic view of a lithium indium alloy, and fig. 7(b) is a schematic view of pure Li metal.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the accompanying drawings:
Li-In for metal negative electrode of lithium battery of the embodiment of the inventionxThe alloy electrode, wherein x is more than or equal to 0.10 and less than or equal to 1.
In the embodiment of the invention, the indium element is introduced into the lithium metal to form the alloy, so that the oxidation tendency of pure lithium metal can be reduced, wherein the molar ratio of the indium foil to the lithium foil is 0.10-1 in the lithium indium rolling process. If the proportion is too small, the formed lithium indium alloy phase is not distributed sufficiently, and the growth of lithium dendrite cannot be effectively inhibited and the efficiency of the battery cannot be improved in the circulating process of the battery; however, if the indium-lithium ratio is too large, too much alloy phase causes a large reduction in the flexibility of the rolled alloy, and the alloy hardens to be unusable as a negative electrode of a lithium battery.
Referring to FIG. 1, in the alloy of the embodiment of the present invention, lithium and indium react under the action of mechanical force to form Li13In3、Li3In、Li2In、Li3In2、Li5In4And the intermediate phases have strong affinity with the metallic lithium, can be used as active sites for lithium deposition, keep the structure unchanged, and promote the lithium to be uniformly inserted and extracted at a very high diffusion speed at the interface of the alloy phases, so that the growth of lithium dendrites is inhibited.
Li-In for lithium battery of the embodiment of the inventionxThe preparation method of the alloy electrode material comprises the following steps:
step 1: in a glove box or a sealed device with water oxygen content meeting the requirement, the indium grains are heated until being melted, and then the surface oxide layer is continuously scraped. Specifically, optionally, the atmosphere of the glove box or the closed container is O2≤0.1ppm，H2O is less than or equal to 0.1 ppm; the number of scraping the oxide layer is 3-10.
Step 2: and casting the molten indium on a cooling device, cooling to room temperature, performing mechanical rolling, and rolling to form indium foil with the thickness of about 100-1000 microns or commercial indium foil with the same size. Specifically, optionally, the cooling device is a plate with a rectangular groove with a certain depth.
And step 3: melting the surface of the lithium foil and removing an oxide layer, casting the molten lithium on a cooling device, cooling to room temperature, and rolling again to form the lithium foil with the thickness of about 100-1000 microns, or adopting commercial lithium foils with the same thickness;
and 4, step 4: and compounding the lithium foil and the indium foil, and performing rolling-folding-rolling repeatedly until the required thickness is achieved.
According to the invention, through mechanical alloying of the metal indium and the lithium, various efficiency and safety problems of the metal lithium in the battery cycle process are improved, and meanwhile, when the alloy cathode is used as an alloy cathode, the first coulombic efficiency and the cycle stability of a lithium-manganese-rich cathode material can be improved, and the discharge specific capacity of the lithium-sulfur battery can also be improved, so that the stability of the battery is improved.
In the embodiment of the invention, the metal indium foil and lithium foil laminated structure is rolled, folded and rolled in half under the pressure of about 30-50 MPa, and the process is repeated for a plurality of times.
During the mechanical rolling process, the connected part of the two metal surfaces forms Li in the alloy electrode serving as the negative electrode of the lithium battery through solid state diffusion13In3、Li3In、Li2In、Li3In2、Li5In4And the like, and the alloy phases have strong lithium affinity, so that more nucleation sites can be provided to effectively promote the uniform nucleation of lithium.
The mesophase compound in the lithium indium alloy cathode is uniformly dispersed to form a three-dimensional interconnected metal network structure, so that the performance of the lithium battery is greatly improved.
The lithium indium alloy cathode has stronger oxidation resistance compared with a pure lithium cathode due to mechanical alloying and existence of a mesophase.
The alloy electrode prepared by the embodiment of the invention has the advantages that the performance of a lithium battery can be greatly improved by the three-dimensional interconnected metal network structure in the alloy cathode, under the current density of 0.1C in a lithium-rich manganese-based positive electrode battery system, the first-circle specific discharge capacity is 299.35mAh/g, which is doubled compared with the existing commercial lithium iron phosphate positive electrode capacity, which is 100mAh/g higher than the existing commercial ternary positive electrode material capacity, the charging and discharging coulombic efficiency is 86.7%, the capacity retention rate after 150 cycles is 82%, and compared with the conventional lithium foil cathode, the first-circle specific discharge capacity is 237.7mAh/g, the charging and discharging coulombic efficiency is 78%, and the capacity retention rate after 150 cycles is only 53%; at a current density of 0.2C in the lithium-sulfur battery system, the capacity retention rate after 100 cycles was 88%, and the decay rate from the first cycle was 0.1%, and similarly, the capacity retention rate after 100 cycles when the lithium sheet was used as the negative electrode was 66%, and the decay rate from the first cycle was 0.26%.
According to the invention, a small amount of lithium indium alloy phase is added into the pure lithium foil, so that the problems of lithium dendrite growth, volume change and unstable solid electrolyte intermediate film in the battery cycle process of the pure lithium cathode are solved.
The embodiment of the invention particularly provides a method for simply preparing a lithium indium alloy cathode, and the method has the advantages of a lithium alloy, promotes the insertion and the separation of lithium ions in the charge-discharge cycle process, slows down the growth of lithium dendrites, and improves the safety of a battery. The invention discloses a method for preparing a lithium indium alloy electrode by mechanical rolling alloying. Lithium and indium produce alloy reaction under the action of mechanical force to form Li13In3、Li3In、Li2In、Li3In2、Li5In4And the intermediate phases have strong affinity with the metallic lithium, can be used as active sites for lithium deposition, keep the structure unchanged, and promote the lithium to be uniformly inserted and extracted at a very high diffusion speed at the interface of the alloy phases, so that the growth of lithium dendrites is inhibited. The invention produces a mechanical alloying effect by repeatedly folding and rolling the metal indium and the lithium at room temperature, and prepares the Li-In alloy foil pole piece. The traditional method for rolling double metals in a laminated way can only prepare one strong metalIn an interface bonded layered composite, the two metals cannot form their mesophase alloy, and if necessary to produce an alloy, the two metals are usually melted to form an alloy. Lithium and indium are low-melting point metals, have larger diffusion coefficients, the interface of the lithium and indium is strongly combined under certain pressure at room temperature, and two metal atoms can cross the interface through mutual diffusion to form intermediate phase alloy, so that the original interface disappears and is fused into integral alloy. When the formed lithium-indium alloy is used as an alloy cathode, the first coulombic efficiency and the cycling stability of the lithium-manganese-rich cathode material can be improved, the specific discharge capacity of the lithium-sulfur battery can be improved, and the stability of the battery can be improved.
Example 1
Li-In for lithium battery of the embodiment of the invention0.154The preparation method of the alloy electrode comprises the following steps:
(1) in an atmosphere of O2≤0.1ppm，H2In a glove box with O less than or equal to 0.1ppm, taking 40mg indium grains to heat and melt, then scraping an oxide layer, casting the oxide layer in a stainless steel plate with a rectangular groove to perform cooling treatment (the depth of the groove is 1mm), and rolling to form indium foil;
(2) in an atmosphere of O2≤0.1ppm，H2In a glove box with O less than or equal to 0.1ppm, taking 70mg of lithium foil, heating to melt, removing a surface oil stain layer, casting the lithium foil in a stainless steel plate with a rectangular groove, cooling (the depth of the groove is 1mm), and finally rolling to form a lithium sheet;
(3) forming a laminated structure of the lithium foil and the indium foil, and performing rolling-folding treatment for several times;
(4) and (4) performing punching sheet treatment on the alloy subjected to the rolling treatment in the step (3) with the diameter of 16mm to serve as a negative electrode material of a lithium battery, and then assembling the battery.
Referring to fig. 2, fig. 2 is a scanning photograph and an element distribution diagram of the lithium indium alloy negative electrode prepared in example 1. Fig. 2(a) shows the appearance of a particulate second phase In pure Li metal of uniform composition, and fig. 2(b) is an elemental distribution diagram showing the non-uniform distribution of the In element, illustrating the occurrence of the second phase, as determined by analysis In conjunction with the Li-In binary metal phase diagram shown In fig. 1: after a plurality of roller pressing treatments, Li appears13In3And waiting for the second phase.
Example 2
Li-In for lithium battery of the embodiment of the invention0.33The preparation method of the alloy electrode comprises the following steps:
(1) in an atmosphere of O2≤0.1ppm，H2In a glove box with O less than or equal to 0.1ppm, 60mg of indium grains are heated and melted, then an oxide layer is scraped, and the indium grains are cast in a stainless steel plate with a rectangular groove for cooling treatment (the depth of the groove is 1mm), and are rolled to form indium foil;
(2) in an atmosphere of O2≤0.1ppm，H2In a glove box with O less than or equal to 0.1ppm, 80mg of lithium foil is taken to remove the surface oil stain layer, then the glove box is placed in a stainless steel plate with a rectangular groove for cooling treatment (the depth of the groove is 1mm), and finally, a lithium sheet is formed by rolling;
(3) forming a sandwich structure by lithium foil and indium foil, and performing rolling-folding treatment for several times;
(4) and (4) performing punching sheet treatment on the alloy subjected to the rolling treatment in the step (3) with the diameter of 16mm to serve as a negative electrode material of a lithium battery, and then assembling the battery.
Referring to fig. 3, fig. 3 is a schematic diagram illustrating a comparison of the first charge-discharge curves of the lithium indium alloy negative electrode prepared in example 2 at 0.1C in a lithium manganese-rich battery system. In the figure, a curve 1 shows that a Li-In alloy electrode is a negative electrode, a curve 2 shows that a button lithium battery which is composed of pure Li metal as the negative electrode, the first discharge capacity of the lithium battery which takes the Li-In alloy as the negative electrode reaches 299mAh/g, and the first discharge capacity of the lithium battery which takes the pure lithium metal as the negative electrode is only 237 mAh/g. In addition, the discharge voltage of the lithium battery taking the Li-In alloy electrode as the negative electrode is obviously higher than that of a pure lithium metal lithium battery.
Example 3
Li-In for lithium battery of the embodiment of the invention0.5The preparation method of the alloy electrode comprises the following steps:
(1) in an atmosphere of O2≤0.1ppm，H2In a glove box with O less than or equal to 0.1ppm, taking 70mg indium grains to heat and melt, then scraping an oxide layer, cooling and rolling;
(2) in an atmosphere of O2≤0.1ppm，H2In a glove box with O less than or equal to 0.1ppm, 100mg of lithium foil is taken to be heated and meltedRemoving the surface oil stain layer, and cooling and rolling;
(3) forming a sandwich structure by lithium foil and indium foil, and performing rolling-folding treatment for several times;
(4) and (4) performing punching sheet treatment on the alloy subjected to the rolling treatment in the step (3) with the diameter of 16mm to serve as a negative electrode material of a lithium battery, and then assembling the battery.
Referring to fig. 4, fig. 4 is a schematic diagram showing the comparison of the cycle performance at 0.5C (voltage window is 2.0-4.8V) of the lithium-indium alloy cathode prepared in example 3 after two cycles of activation at 0.1C in a lithium-manganese-rich battery system; the results show that the lithium battery with the Li-In alloy negative electrode composition has higher cycle stability and capacity than the lithium battery with pure metal lithium as the negative electrode.
Example 4
Li-In for lithium battery of the embodiment of the invention0.66The preparation method of the alloy electrode comprises the following steps:
(1) in an atmosphere of O2≤0.1ppm，H2In a glove box with O less than or equal to 0.1ppm, taking 80mg indium grains to heat and melt, then scraping an oxide layer, cooling and rolling;
(2) in an atmosphere of O2≤0.1ppm，H2Weighing 110mg of lithium foil in a glove box with O less than or equal to 0.1 ppm;
(3) forming a sandwich structure by lithium foil and indium foil, and performing rolling-folding treatment for several times;
(4) and (4) performing punching sheet treatment on the alloy subjected to the rolling treatment in the step (3) with the diameter of 16mm to serve as a negative electrode material of a lithium battery, and then assembling the battery.
Referring to fig. 5, fig. 5 is a graph illustrating a first charging/discharging curve of the lithium indium alloy negative electrode prepared in example 4 at 0.05C in a lithium sulfur battery system. The result shows that the initial discharge capacity of the Li-S battery formed by the Li-In alloy negative electrode and the S is also obviously superior to that of pure Li metal.
Example 5
Li-In for lithium battery of the embodiment of the invention0.8The preparation method of the alloy electrode comprises the following steps:
(1) in an atmosphere of O2≤0.1ppm，H2Glove with O less than or equal to 0.1ppmIn a box, 100mg of indium grains are taken to be heated and melted, then an oxide layer is scraped, and the indium grains are cooled and then rolled;
(2) in an atmosphere of O2≤0.1ppm，H2Weighing 130mg of lithium foil in a glove box with O less than or equal to 0.1 ppm; (3) forming a sandwich structure by lithium foil and indium foil, and performing rolling-folding treatment for several times;
(4) and (4) performing punching sheet treatment on the alloy subjected to the rolling treatment in the step (3) with the diameter of 16mm to serve as a negative electrode material of a lithium battery, and then assembling the battery.
Referring to fig. 6, fig. 6 is a schematic diagram showing the comparison of the cycle performance of 0.2C (voltage window of 1.7-2.8V) after the lithium indium alloy cathode prepared in example 5 is activated for two cycles at 0.05C and 0.1C in a lithium sulfur battery system. The results show that the Li-In alloy negative electrode and the Li-S battery composed of S are also obviously superior to the Li-S battery of the lithium metal negative electrode In cycle writing.
Example 6
Li-In for lithium battery of the embodiment of the invention0.22The preparation method of the alloy electrode comprises the following steps:
(1) in an atmosphere of O2≤0.1ppm，H2In a glove box with O less than or equal to 0.1ppm, 50mg of indium grains are taken to be heated and melted, then an oxide layer is scraped, and the mixture is cooled and rolled;
(2) in an atmosphere of O2≤0.1ppm，H2Weighing 90mg of lithium foil in a glove box with O less than or equal to 0.1 ppm;
(3) forming a sandwich structure by lithium foil and indium foil, and performing rolling-folding treatment for several times;
(4) and (4) performing punching sheet treatment on the alloy subjected to the rolling treatment in the step (3) with the diameter of 16mm to serve as a negative electrode material of a lithium battery, and then assembling the battery.
Referring to fig. 7, fig. 7 is a graph comparing the lithium indium alloy prepared in example 6 and a pure lithium foil after being placed in air for five minutes to resist oxidation. The result shows that the room temperature atmospheric oxidation resistance of the Li-In alloy cathode is obviously superior to that of a pure Li metal cathode.
In summary, the embodiment of the invention discloses Li-In for a lithium batteryxThe alloy electrode and the preparation method thereof comprise the following steps: in an atmosphere of O2≤0.1ppm，H2Heating and melting indium particles in a closed container with O less than or equal to 0.1ppm, scraping an oxide layer, placing the indium particles in a plate with a rectangular groove with a certain depth, and performing rolling treatment; heating and melting the lithium foil, removing the oil stain layer on the surface, placing the lithium foil in a plate with a rectangular groove with a certain depth, cooling, and rolling; taking a sandwich structure formed by lithium foil and indium foil, and performing rolling-folding treatment for several times; and (4) performing punching sheet treatment on the rolled alloy with the diameter of 16mm to obtain the negative electrode material of the lithium battery. The Li-In prepared by the simple mechanical rolling method of the inventionxThe alloy electrode negative electrode material effectively reduces the growth of lithium dendrites, improves the safety of the battery, simultaneously has simple operation and cost saving, and shows excellent electrochemical performance. More specifically, according to the technical solution of the embodiment of the present invention, a small amount of lithium indium alloy phase is added to a pure lithium foil, so as to improve the problems of lithium dendrite growth, continuous volume change and unstable intermediate film of a solid electrolyte in the battery cycle process of a pure lithium negative electrode.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the above embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the embodiments of the invention without departing from the spirit and scope of the invention, which is to be covered by the claims.
Claims (9)
1. The lithium indium alloy negative electrode material for the lithium battery is characterized in that the molar ratio of indium to lithium in the lithium indium alloy negative electrode material is 0.10-1, and the intermediate phase comprises Li13In3、Li3In、Li2In、Li3In2And Li5In4One or more of (a).
2. The lithium indium alloy negative electrode material for a lithium battery as claimed in claim 1, wherein the mesophase serves as an active site for lithium deposition.
3. The lithium indium alloy negative electrode material for a lithium battery as claimed in claim 1, wherein, in the lithium indium alloy negative electrode material, the intermediate phase forms a three-dimensional interconnected metal network structure.
4. A preparation method of a lithium indium alloy cathode material for a lithium battery is characterized by comprising the following steps:
obtaining indium foil and lithium foil with preset thicknesses;
compounding the obtained lithium foil and indium foil to form a laminated structure, and performing rolling-folding-rolling repeatedly in a preset pressure range until the preset required thickness is reached to obtain a lithium indium alloy cathode material for a lithium battery;
the molar ratio of indium to lithium in the obtained lithium-indium alloy cathode material for the lithium battery is 0.10-1; the rolling-folding-rolling is carried out within a preset pressure range and is used for forming Li13In3、Li3In、Li2In、Li3In2And Li5In4One or more mesophases.
5. The method for preparing the lithium-indium alloy negative electrode material for the lithium battery as claimed in claim 4, wherein the step of obtaining indium foil and lithium foil with preset thicknesses specifically comprises:
under the working condition that the water oxygen content meets the preset requirement, heating and melting indium, and scraping a surface oxide layer to obtain molten indium; casting the molten indium into a cooling device, cooling to room temperature, performing mechanical rolling until the thickness is 100-1000 microns, and obtaining indium foil with a preset thickness;
melting the lithium foil and removing the oxide layer to obtain molten lithium; and casting the molten lithium into a cooling device, cooling to room temperature, performing mechanical rolling until the thickness is 100-1000 microns, and obtaining the lithium foil with the preset thickness.
6. The method for preparing the lithium-indium alloy anode material for the lithium battery as claimed in claim 4, wherein the predetermined pressure is in a range of 30 to 50 MPa.
7. The method for preparing the lithium-indium alloy negative electrode material for the lithium battery as claimed in claim 4, wherein the rolling-folding-rolling is performed under a predetermined pressure range, so as to form the three-dimensional interconnected metal network structure of the intermediate phase.
8. A lithium battery, characterized in that the lithium indium alloy negative electrode material according to any one of claims 1 to 3 is used for a negative electrode of the lithium battery.
9. A lithium battery, characterized in that the negative electrode of the lithium battery adopts the lithium indium alloy negative electrode material prepared by the preparation method of any one of claims 4 to 7.
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