CN111430720B - Electrode protective layer and preparation method thereof, electrode and lithium battery - Google Patents
Electrode protective layer and preparation method thereof, electrode and lithium battery Download PDFInfo
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- CN111430720B CN111430720B CN201910024641.3A CN201910024641A CN111430720B CN 111430720 B CN111430720 B CN 111430720B CN 201910024641 A CN201910024641 A CN 201910024641A CN 111430720 B CN111430720 B CN 111430720B
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- 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 relates to the technical field of lithium batteries, and discloses an electrode protection layer, a preparation method thereof, an electrode and a lithium battery. The electrode protection layer contains lithium, and the molar content of the lithium is different in the thickness direction of the electrode protection layer; the electrode protection layer further comprises a first element M and a second element D; the first element M can form an alloy with lithium, the second element D cannot form an alloy with lithium, and the first element M and the second element D can form an alloy. The electrode protection layer provided by the invention can be used for prolonging the cycle life and improving the stability of the lithium battery.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to an electrode protection layer, a preparation method thereof, an electrode and a lithium battery.
Background
The lithium ion battery has the advantages of high energy density and convenience, gradually obtains market approval through the development of twenty years, and realizes large-scale application in the fields of personal electronic equipment, electric automobiles and the like. Among the known electrode materials, the lithium metal negative electrode has a mass of 3860mAh g-1The high capacity and most negative potential (-3.040V vs. standard hydrogen electrode) become the "holy cup" of the energy storage community, and are of interest to researchers. In the 70 s of the 20 th century, lithium metal primary batteries have been commercialized in various fields such as cardiac pacemakers, space exploration and oil exploration. However, when the lithium metal is used as the negative electrode of the secondary battery, lithium dendrites are easily formed by reversible deposition of lithium, and individual lithium dendrites pierce through the separator, so that the internal short circuit of the battery is caused, and potential safety hazards are formed. The inhibition of dendrite growth is the key to realizing the large-scale application of the high-energy density lithium metal battery.
In order to inhibit dendrite growth and improve the safety, utilization and cycle life of lithium metal batteries, scientists have proposed a variety of solutions in the past half century.
US49091152A discloses an electrolyte and an additive for avoiding dendrite formation during lithium deposition, wherein the additive for avoiding dendrite formation during lithium deposition in a non-aqueous electrolyte, especially an organic electrolyte, is a metal ion which can be reduced by lithium and form a lithium metal or an alloy.
US6733924B1 discloses a lithium negative electrode for an electrochemical cell having a first layer of lithium metal and a second layer of a temporary protective material which can be alloyed with or diffused into the lithium metal.
US6955866B2 discloses a lithium anode protected with a metal-lithium alloy and a battery comprising the anode. The negative electrode takes lithium as a core, firstly a layer of inert metal is deposited on the surface of the lithium, then a layer of active metal is deposited, a coated ternary alloy layer is formed on the surface of the lithium negative electrode, lithium in the ternary alloy layer comes from the lithium electrode, and the degree of lithiation is not easy to control. The lithium cathode protection technology based on the alloy improves the capacity retention rate and the cycling stability. However, the invention only shows the 20-week cycle results of a common binary alloy, and although the feasibility of the alloy as a lithium metal negative electrode protective layer is illustrated, the long cycle life and stability of the negative electrode are not guaranteed. And, the Li-Al alloy used therein undergoes significant volume expansion and contraction during electrochemical cycling.
US9722275B2 discloses a battery comprising: (a) an active metal or a material capable of storing metal ions (such as an intercalation compound capable of storing lithium ions) is taken as a negative electrode; (b) a positive electrode structure; (c) and the negative electrode surface protection layer with ion conduction capability is positioned between the positive electrode structure and the negative electrode structure.
In the prior art, metal alloy is mostly used as a substitute electrode of lithium metal, and during lithiation of an alloy electrode, due to introduction of lithium, significant volume expansion occurs, and during delithiation, significant shrinkage occurs. The repeated charge and discharge process is accompanied by repeated volume expansion and contraction, so that the electrode structure is gradually damaged, the alloy electrode finally falls off from the battery, the performance of the battery is attenuated and even finally loses efficacy, and the cycle life and the stability of the battery are influenced.
Disclosure of Invention
The invention aims to solve the problems of short cycle life and poor stability of a lithium battery in the prior art, and provides an electrode protection layer, a preparation method thereof, an electrode and a lithium battery. The electrode protection layer is introduced into the negative electrode of the lithium battery, so that the cycle life and the stability of the lithium battery can be improved.
In order to achieve the above object, a first aspect of the present invention provides an electrode protective layer containing lithium, and having a difference in molar content of lithium in a thickness direction of the electrode protective layer; the electrode protection layer further comprises a first element M and a second element D; the first element M can form an alloy with lithium, the second element D cannot form an alloy with lithium, and the first element M and the second element D can form an alloy.
In a second aspect, the present invention provides a method for preparing the electrode protection layer according to the first aspect of the present invention, the method comprising:
1) preparing an alloy containing a first element M and a second element D and having a plurality of crystallinities;
2) performing electrochemical lithiation on the alloy obtained in the step 1) to obtain the electrode protection layer.
The third aspect of the present invention provides an electrode, which includes a current collector and an electrode protection layer wrapped on the surface of the current collector, where the electrode protection layer is the electrode protection layer according to the first aspect of the present invention.
In a fourth aspect, the invention provides a lithium battery, the negative electrode of which is the electrode of the third aspect.
Through the technical scheme, the cycle life and the stability of the lithium battery can be improved.
Drawings
FIG. 1 is a schematic view of an electrode protection layer in a preferred embodiment of the present invention;
FIG. 2 is a schematic view of a portion of the alloy composition in which three elements Li, Co, Sn can be formed;
FIG. 3 is a schematic view of an electrode protection layer in another preferred embodiment provided by the present invention;
FIG. 4 is a schematic view of an electrode protection layer in yet another preferred embodiment provided by the present invention;
FIG. 5 is a schematic illustration of the deposition and electrochemical lithiation processes in the examples;
FIG. 6 is a graph of experimental results of electrochemical lithiation of alloy thin films obtained at different deposition temperatures;
FIG. 7 is a process of lithium extraction from the ternary alloy layer, with metallic lithium as the counter electrode;
FIG. 8 is a process of lithium incorporation in a ternary alloy layer, with metallic lithium as the counter electrode;
fig. 9 is a charge and discharge diagram (#1) of a battery using a lithium metal electrode of an electrodeless protective layer as an electrode and a charge and discharge diagram (#2) of a battery using the electrode in the examples as an electrode.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The first aspect of the present invention provides an electrode protective layer containing lithium, the molar content of which differs in the thickness direction of the electrode protective layer; the electrode protection layer further comprises a first element M and a second element D; the first element M can form an alloy with lithium, the second element D cannot form an alloy with lithium, and the first element M and the second element D can form an alloy.
In the present invention, the molar content of lithium means a molar percentage of lithium based on the total amount of lithium, the first element M, and the second element D at a certain fixed thickness of the electrode protection layer. Unless otherwise specified, the molar content of the first element M and the molar content of the second element D are defined as the molar content of lithium.
The electrode protection layer provided by the invention has different lithium molar contents in the thickness direction, and the structure is different from a protection layer structure with uniformly distributed lithium molar contents, so that the concentration gradient of lithium can be formed in a certain direction, and the diffusion process of lithium ions can be enhanced.
The "second element D is not alloyed with lithium" means that the second element D is not alloyed with lithium in the case where only the second element D and lithium are present and no other element is present.
Preferably, the electrode protection layer contains Li of the general formulaxDyMzTwo or more of the alloys represented, wherein x, y and z are in molar amounts.
According to a preferred embodiment of the present invention, the electrode protection layer includes at least two sub-alloy layers containing the alloy, the sub-alloy layers are stacked, and the first element M is the same element between the sub-alloy layers and has different molar contents. The second element D between the sub-alloy layers can be the same or different elements, and the molar content can be the same or different.
According to another preferred embodiment of the present invention, the electrode protection layer is a layer including at least two sub-alloy layers containing the alloy, the sub-alloy layers are stacked, and the first element M between the sub-alloy layers is selected from different elements, and the molar contents thereof may be the same or different. The second element D between the sub-alloy layers can be the same or different elements, and the molar content can be the same or different.
In the present invention, the first element M is an element capable of forming an alloy with lithium metal. In the charge and discharge process of the lithium battery, the first element can provide a channel for migration of lithium atoms or lithium ions, and the lithium atoms or the lithium ions can migrate in and out of two phases of solid-phase and liquid-phase electrolytes of the electrode. Preferably, the first element is selected from at least one of Al, Si, P, Ga, Ge, As, Ag, Cd, In, Sn, Sb, Au, Pb, Bi, Zn, Mg.
In the present invention, the second element D is an element that cannot form an alloy with lithium metal. In the charging and discharging process of the lithium battery, the second element does not react or interact with lithium, and the structural integrity of the electrode is favorably maintained. Preferably, the second element is at least one selected from Cu, Ni, Co, Fe, Mn, Cr, V, Ti, Mo, W.
Preferably, the thickness of the electrode protection layer is 10nm to 100 μm.
Several preferred embodiments of the invention are provided below:
the electrode protective layer of the invention is obtained by combining metal, metalloid and nonmetal elements to obtain a ternary alloy layer, such as a sub-alloy layer formed by Li, Co and Sn and containing two or more layers containing the above elements, the schematic diagram of which is shown in FIG. 1, and part of alloy components formed by Li, Co and Sn can be shown in FIG. 2.
(II) combining metal, metalloid and nonmetal elements to obtain a quaternary alloy layer as the electrode protection layer according to the invention, such as a sub-alloy layer formed by Li, Co, Cu and Sn and containing two or more layers containing the above elements, and the schematic diagram is shown in FIG. 3.
And (III) combining metal, metalloid and nonmetal elements to obtain a quinary alloy layer as the electrode protection layer, such as Li, Co, Cu, Sn, In, which is formed by two or more sub-alloy layers containing the above elements, and the schematic diagram is shown In FIG. 4.
A second aspect of the present invention provides a method of protecting an electrode according to the first aspect of the present invention, the method comprising:
1) preparing an alloy containing a first element M and a second element D and having a plurality of crystallinities;
2) performing electrochemical lithiation on the alloy obtained in the step 1) to obtain the electrode protection layer.
Preferably, the method of preparing the alloy in step 1) comprises: the first element M and the second element D are simultaneously deposited at different deposition temperatures. Preferably, the deposition temperature is in the range of 20-200 ℃. The different deposition temperatures may for example comprise three different deposition temperatures of 25 ℃, 100 ℃ and 200 ℃, by varying the temperature during deposition an alloy with different crystallinity is obtained.
In the present invention, the alloy may be prepared by depositing the first element M and the second element D on the surface of a current collector, which may be, for example, Li, Cu, Ni, Co, or the like.
Preferably, the deposition method is selected from one of vacuum magnetic sputtering, direct current sputtering, radio frequency sputtering and evaporation sputtering.
According to a preferred embodiment of the present invention, the method of preparing the alloy in step 1) further comprises: the molar content of the first element M is varied during the deposition. In this preferred embodiment, the molar content of the first element M refers to the molar percentage of the first element M based on the total amount of the first element M and the second element D.
According to another preferred embodiment of the present invention, the method of preparing the alloy in step 1) further comprises: the species of the first element is changed during the deposition process.
In the present invention, electrochemical lithiation is carried out on a battery assembled by introducing the alloy obtained in step 1) into a positive electrode of a lithium battery and then a negative electrode containing lithium metal, and the electrolyte in the battery can be a commercial electrolyte, for example, a 1M solution of LiPF6 in ethylene carbonate/dimethyl carbonate (volume ratio 1: 1). The introduction of lithium into the alloy obtained in step 1) is achieved by migration of lithium during electrochemical lithiation. In the invention, the molar content of lithium can be represented by the content of introduced lithium in the alloy, and the lithium capacity in the electrochemical lithiation process is proportional to the molar content of lithium in the finally obtained alloy.
Preferably, the electrochemical lithiation is carried out at a lithiation current of 0.01 to 100mA for a lithiation time of 1min to 10 h.
The third aspect of the present invention provides an electrode, including a current collector and an electrode protection layer wrapped on the surface of the current collector, where the electrode protection layer is the electrode protection layer according to the first aspect of the present invention.
In the invention, the electrode is obtained by preparing the electrode protection layer on the surface of the current collector. The current collector refers to a material capable of conducting electricity. Preferably, the current collector is selected from one of Li, Cu, Ni, Co, Fe, Mn, Cr, V, Ti, Mo and W.
In a fourth aspect, the invention provides a lithium battery, the negative electrode of which is the electrode of the third aspect.
In the present invention, the lithium battery may be assembled by a method commonly used in the art, including: and a negative electrode and a positive electrode are respectively arranged at two sides of the diaphragm, and electrolyte is added, wherein the negative electrode is the electrode disclosed by the invention.
In the present invention, the positive electrode may be a positive electrode commonly used in the art, and may be commercially available. Preferably, the positive electrode of the lithium battery is a transition metal oxide of lithium. More preferably, the transition metal oxide of lithium is selected from LiCoO2、LiNiaMnbCocO2、LiNidCoeAlfO2、LiFePO4And LiNimMnnO2Wherein the values of a, b, c, d, e, f, m, n depend on the different formulations of the commercial product.
In the present invention, the electrolyte may be an electrolyte commonly used in the art, and may be commercially available, for example, lithium hexafluorophosphate (LiPF)6) A solution in a carbonic acid type solvent (e.g., ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propylene carbonate, or a mixed solvent thereof), or a solution of lithium bistrifluoromethanesulfonylimide in dimethoxyethane and dioxolane, or other commercially available electrolytes, comprising a lithium salt and an organic solvent.
In the present invention, the separator is a separator commonly used in the art, is commercially available, and may be a polymer film, an inorganic film, or a composite of both, and the present invention is not particularly limited thereto.
The lithium battery of the present invention may be in various forms such as a pillar or a pouch, and the present invention is not particularly limited thereto.
The present invention will be described in detail below by way of examples.
Examples
1) And preparing the Co-Sn alloy. A high vacuum magnetron sputtering apparatus (available from AJA) was used, and the chamber contained three 1.5 inch diameter tips connected in pairs to form a triangular shape. The vacuum was controlled at 10-8Torr, and three different deposition temperatures were successively applied to a 50 μm thick copper foil: sequentially growing the laminated CoSn with different crystallinities at room temperature (25 ℃), 100 ℃ and 200 DEG C2And (3) an alloy film. The sputtering power used was 45-75W. Alloy thin films each having a thickness of about 250nm were obtained by deposition on 50 μm copper foil for 10 minutes at each deposition temperature.
2) The copper foil having the Co-Sn alloy layer was cut into a wafer having a diameter of 15 mm. Alloy disks and lithium metal plates (diameter 15mm, available from Sigma-Aldrich) were assembled as electrodes in CR2032 coin cells (available from Pred Materials) using a microporous Celgard separator (25 μ M, polypropylene/polyethylene/polypropylene tri-layer structure, available from shenzhencaojing) with an electrolyte of 1M ethylene carbonate/dimethyl carbonate (volume ratio 1:1, available from motion) solution of LiPF 6.
The lithiation current of the alloy layer was 0.05mA (0.028 mA/cm)-2) The voltage interval is from the open circuit potential to 0V.
Deposited with CoSn2The copper foil of the binary alloy layer is converted into a ternary alloy Li after lithium is added by an electrochemical methodxCoSn2And obtaining the electrode protection layer, wherein the process schematic diagram is shown in fig. 5.
Test example
Separately preparing CoSn with a thickness of 252nm and different crystallinity at different deposition temperatures according to the method of step 1)2The alloy films were then separately electrochemically lithiated (lithiation current 0.05mA), and the experimental results are shown in FIG. 6, in which curve A shows the transfer of lithium ions from Li to CoSn deposited at room temperature (25 ℃ C.)2Alloying; curve B shows the transfer of lithium ions from Li to CoSn deposited at 100 deg.C2Alloying; curve C represents the transfer of lithium ions from Li to CoSn deposited at 200 deg.C2And (5) alloying. As can be seen from the difference between the curves A, B and C in the figure, the lithium capacities of the alloy thin films with different crystallinities obtained at different deposition temperatures after lithiation are different, that is, the lithium contents in the obtained ternary alloys are different, thereby illustrating that the lithium contents in the thickness direction of the electrode protection layers obtained in the examples are different.
Li formed after lithiationxCoSn2The ternary alloy layer can transport lithium ions during electrochemical cycling.
Lithium is derived from a ternary alloy layer (CoSn obtained at a deposition temperature of 100℃)2Ternary alloy layer obtained by lithiation of the alloy) causes an increase in voltage (metal lithium for the counter electrode), as shown in fig. 7, indicating that lithium ions are separated from LixCoSn2Transfer to Li. If the counter electrode is a high voltage positive electrode, e.g. LiCoO2The voltage is reduced from 4.2V to about 3V. This is equivalent to LiCoO2The high voltage electrode is used as a positive electrode and is provided with a protective layer (such as Li)xCoSn2) The battery having the lithium metal as a negative electrode is subjected to a discharge process.
FIG. 8 shows lithium in a ternary alloy layer (CoSn obtained for a deposition temperature of 100 ℃ C.)2Ternary alloy layer obtained after lithiation of the alloy), i.e. transfer of lithium ions from Li to LixCoSn2The counter electrode used in the process of (1) is metallic lithium.
Assembling process of the lithium symmetrical battery: two lithium metal electrodes were placed on either side of a separator filled with a liquid electrolyte (1M ethylene carbonate/dimethyl carbonate solution of LiPF6, volume ratio of two organic solvents 1: 1). The battery was continuously charged/discharged at a fixed current of 0.05mA, after a fixed time, a reverse current was applied and maintained for the same time, and then the above procedure was repeated at currents of 0.25mA, 0.5mA and 0.88 mA.
In this process, the change of voltage with time was recorded, wherein, as shown in fig. 9, #1 used was a lithium metal electrode as an electrodeless protection layer; #2 used was the lithium metal electrode having the electrode protective layer obtained in example.
As can be seen from fig. 9, the electrode with the electrode protection layer provided by the present invention has a longer cycle life and better stability than the lithium electrode without the electrode protection layer.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
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