CN112701344B - LiAl5O8Preparation method of nanowire, composite solid electrolyte and lithium metal battery - Google Patents
LiAl5O8Preparation method of nanowire, composite solid electrolyte and lithium metal battery Download PDFInfo
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Abstract
The invention discloses a LiAl5O8Preparation method of nanowire, composite solid electrolyte, lithium metal battery and LiAl5O8The preparation method comprises the following steps: for Al (EtO)3Pre-calcining the nanowires, and then putting the pre-calcined Al (EtO) in a protective atmosphere3Soaking the nanowire film in a lithium ion solution; after the soaking, solid-liquid separation is carried out to obtain Al (EtO) for supplementing lithium3A nanowire; calcining the lithium-supplemented Al (EtO)3Nanowire to obtain LiAl5O8A nanowire. The LiAl of the invention5O8The composite solid electrolyte prepared by the nano-wire can guide Li+Deposition in lamellar rather than dendritic form can significantly improve the long cycle stability and rate capability of lithium metal batteries.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to a LiAl5O8A preparation method of the nanowire, a composite solid electrolyte and a lithium metal battery.
Background
The rapid development of portable electronic devices, electric vehicles, and energy storage power grids has driven the development of secondary batteries with high energy density. Lithium metal batteries having high theoretical specific capacity (3860mAh g) due to the lithium metal (Li) negative electrode-1) Low density (0.59g cm)-3) And low reduction potential (minus 3.04V compared with standard hydrogen potential), so that it is a secondary battery with high specific energy density and wide application prospect[1]. However, in practical applications, the development of lithium metal batteries is severely limited by unstable electrolyte membranes (SEI films) and uncontrolled dendrite growth in liquid organic electrolytes. First, lithium metal has a serious volume change during deposition and dissolution, and it is difficult to form a stable SEI film. Therefore, the electrolyte reacts with the lithium metal repeatedly, resulting in low coulombic efficiency and rapid capacity drop. Secondly, lithium dendrites form during charging and discharging due to non-uniform deposition of lithium, leading to increased formation of "dead lithium" and polarization, and even penetrationThe battery separator contacts the cathode to cause internal short-circuiting of the battery, thereby causing thermal runaway and even explosion[2]. Therefore, these obstacles must be eliminated to achieve safety, high coulombic efficiency, and long cycle life of the lithium metal battery.
In recent years, researchers have made extensive efforts to solve the above problems, such as optimizing the composition of the electrolyte[3-6]Constructing an interface protection layer[7-10]And constructing a three-dimensional composite lithium metal negative electrode[11-14]. In addition, the rapid development of solid electrolytes provides an important solution to the safety problem of lithium metal batteries because the solid electrolytes have high shear modulus and hardness, and are expected to resist the intrusion of lithium dendrites[15]. Solid electrolyte types including oxides, sulfides, thin films and polymers[16]. Oxide solid electrolytes such as Li3.3La3Zr2O12(LLZO) and Li3.3La0.56TiO3(LLTO), which has been widely studied because of its high ionic conductivity, high mechanical strength, and good electrochemical stability. But also face the problems of high energy consumption, non-uniformity, instability to moisture and carbon dioxide in air and the like. Therefore, it is necessary to develop a novel solid electrolyte which is low in cost, simple in synthesis and convenient in storage. Furthermore, solid-state electrolytes typically reduce to more stable compounds when in direct contact with lithium metal. For example, according to the first principles of Density Functional Theory (DFT), the reduction limit of LLZO is 0.05V (or 0.07V), and the possible reduction products of LLZO are Zr and La2O3、Li8ZrO6、Zr3O and Li2O[18,19]. Most of previous research works adopt strategies such as coating and the like[20,21]So as to avoid side reaction of the solid electrolyte on the interface, and the solid electrolyte is suitable for the solid lithium metal battery. However, there are few examples of directly improving the interfacial compatibility of the solid electrolyte and lithium metal by using byproducts.
LiAl5O8Has been used as a phosphor having optical characteristics[22]And was once detected in the aluminum oxide coating between the lithium metal negative electrode and the garnet-type solid electrolyte[23]. Recently, LiAl has been proposed according to DFT calculations5O8Is a lithium ion (Li) with high lithium ion content+) Potential lithium ion conductors of mobility. The calculations indicate that lithium interstitials are the predominant diffusion carrier at low electrode potentials, while lithium vacancies are the predominant diffusion carrier at high electrode potentials. By calculation prediction, LiAl5O8The stable voltage range of the coating is 0.08-4.08V vs Li/Li+. When the voltage is lower than 0.8V, LiAl5O8Can be reduced into aluminum (Al) and further form Li at lower voltagexAlyAnd (3) alloying. A large number of studies prove that Al can induce Li+Uniformly deposited on the Li metal cathode, thereby inhibiting the growth of Li dendrite[25-27]. However, without effective regulation, these serious side effects can destroy LiAl5O8The solid electrolyte is in contact with the interface of the electrodes. In fact, LiAl5O8The above-mentioned side reactions have not been confirmed in experiments because it is difficult to prepare the material by the conventional solid phase sintering method[28]. Therefore, a large-scale production of LiAl was developed5O8Then carefully adjusting the LiAl5O8It is important that the interface of the solid-state electrolyte and the lithium metal negative electrode significantly reduce side reactions.
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disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a LiAl5O8The preparation method of the nano wire can successfully prepare LiAl5O8Nano wire, simple operation and strong universality.
The invention also provides a composite solid electrolyte and a lithium metal battery.
Specifically, the technical scheme adopted by the invention is as follows:
in a first aspect of the present invention, there is provided a LiAl5O8The preparation method of the nanowire comprises the following steps:
for Al (EtO)3Pre-calcining the nanowires, and then putting the pre-calcined Al (EtO) in a protective atmosphere3Soaking the nano-wire in a lithium ion solution;
after the soaking, solid-liquid separation is carried out to obtain Al (EtO) for supplementing lithium3A nanowire;
calcining the lithium-supplemented Al (EtO)3Nanowire to obtain LiAl5O8A nanowire.
The lithium ion solution comprises lithium ethoxide (EtOLi) solution and lithium phosphate (Li)3PO4) Solution, lithium perchlorate (LiClO)4) Solution, lithium carbonate (Li)2CO3) Solution, lithium methoxide (CH)3OLi) at least one of the solutions.
The concentration of lithium ions in the lithium ion solution is 0.1-0.5M.
The Al (EtO)3The mass ratio of the nanowire to the lithium ion solution is 1: 500-700, preferably 1: 625.
The soaking time is 2-20 min, preferably 5 min.
The LiAl5O8In the preparation method of the nanowire, the pre-calcining temperature is 300-500 ℃, and preferably 400 ℃; the pre-calcining time is 5-15 min. Al (EtO)3The nanowire can be broken and dissolved when being directly soaked in the solution, and can be prevented from being broken and dissolved by being soaked in the lithium ion solution after being pre-calcined, so that the nanowire has a key effect on maintaining the shape of the nanowire.
The calcination (calcination of the lithium-supplemented Al (EtO)3Nanowire) at a temperature of 800-1500 ℃, preferably 1000-1200 ℃; the calcination time is 1-4 h.
More specifically, the calcination process may be carried out according to the following procedure: firstly, the temperature is 0.5-1.5 ℃ per minute-1The temperature rise rate is from room temperature to 500-600 ℃, and then 4-6 ℃ per minute-1Raising the temperature to 800-1500 ℃, preserving the heat for 1-4 h, and then naturally cooling.
The Al (EtO)3The nanowires may be a nanowire film. When said Al (EtO)3LiAl prepared when the nano-wire is a nano-wire film5O8The nanowires also maintain the morphology of the nanowire film.
The Al (EtO)3The nanowire film is made of Al (EtO)3Nanowire gel formation.
More specifically, the Al (EtO)3The nanowire film is prepared by the following steps of3The nanowire gel was suction filtered to form a membrane.
The Al (EtO)3The nanowire gel is prepared by a room temperature dealloying method. More specifically, the Al (EtO)3The preparation method of the nanowire gel comprises the following steps: mixing aluminum and lithium, and calcining to obtain a Li-Al alloy; soaking the Li-Al alloy in ethanol, and heating to react to obtain Al (EtO)3Nano meterA wire gel.
The molar ratio of the aluminum to the lithium is 1: 1-1.5.
Preparation of the Al (EtO)3In the method of nanowire gel, the calcining temperature is 600-1000 ℃, preferably 750-850 ℃; the calcination time is 20-60 min.
The temperature of the heating reaction after the Li-Al alloy is soaked in ethanol is 50-80 ℃, and is preferably 55-65 ℃; the heating reaction time is 20-40 h.
A second aspect of the present invention is to provide a composite solid electrolyte containing the above LiAl5O8A nanowire.
The composite solid electrolyte contains the LiAl5O8Nanowires and a conductive gel polymer encapsulating the LiAl5O8A nanowire.
The composite solid electrolyte also contains lithium salt, and the lithium salt is dispersed in the LiAl5O8Nanowires and conductive gel polymers.
The conductive gel polymer comprises at least one of polyacrylonitrile, polyoxyethylene, polyoxypropylene, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), polymethacrylate and polyacrylonitrile, and preferably the vinylidene fluoride-hexafluoropropylene copolymer.
The lithium salt includes lithium hexafluorophosphate (LiPF)6) Lithium phosphate (Li)3PO4) Lithium perchlorate (LiClO)4) Lithium carbonate (Li)2CO3) Lithium ethoxide (EtOLi), lithium methoxide (CH)3OLi).
A third aspect of the present invention provides a method for preparing a composite solid electrolyte, comprising the steps of: subjecting the LiAl to5O8Soaking the nano-wire in a conductive gel polymer solution, and drying to obtain a conductive gel polymer coated LiAl5O8A film of nanowires a; and (3) enabling the film a to absorb a lithium salt solution to obtain the composite solid electrolyte.
The mass concentration of the conductive gel polymer is 5-15%.
The concentration of the lithium salt solution is 0.5-1.5M.
The invention also provides a lithium metal battery which contains the composite solid electrolyte.
The invention has the following beneficial effects:
(1) the invention uses Al (EtO)3The nano wire is used as a raw material, and the LiAl can be successfully prepared by simple soaking and calcining5O8Nanowires, resulting LiAl5O8The purity of the nano-wire is high, and the Al (EtO) is kept3The nanowire morphology of the nanowire; meanwhile, the invention prepares LiAl5O8The method of the nanowire has the advantages of low cost, simple operation and strong universality.
(2) The composite solid electrolyte has conductive gel polymer coated LiAl5O8The structure of the nanowire is applied to a lithium metal battery taking lithium metal as an electrode, so that interface damage caused by excessive reaction of the lithium metal electrode and an electrolyte is avoided, and a beneficial Al layer is generated on the interface of the composite solid electrolyte and the lithium metal electrode. The Al layer has good wettability to lithium metal and can form uniform Li nuclei on Al sites. Further, LiAl in the composite solid electrolyte5O8Dense LiAl with nanowire morphology5O8The nano-wire has a large number of ion conduction channels and can disperse Li+And flow, and uniform distribution is realized. Based on these two advantages, the composite solid electrolyte of the present invention can guide Li+Deposited in lamellar rather than dendritic form. Therefore, the long-cycle stability and rate capability of the lithium metal battery can be remarkably improved by using the composite solid electrolyte of the present invention.
Drawings
FIG. 1 shows LiAl5O8A flow chart for the preparation of nanowire films;
FIG. 2 shows LiAl5O8XRD pattern of nanowire film;
FIG. 3 shows LiAl5O8SEM images of nanowire films;
FIG. 4 is a morphology of Li deposition on Cu foil in Cu/Li cells assembled from LPH-GPE and APH-GPE;
FIG. 5 shows SEI film morphology in LFP/Li cells assembled from LPH-GPE and APH-GPE;
FIG. 6 is a long-term cycle performance graph of an LFP/Li battery assembled from LPH-GPE and APH-GPE.
Detailed Description
The technical solution of the present invention is further described below with reference to specific examples.
Raw materials: aluminum powder (99.5%), Li particles (99.9%), ethanol (>99.8%, molecular biology), PVDF-HFP (Mw ═ 40 ten thousand) were purchased from alatin. Acetone (HPLC) was purchased from guangzhou chemical industries. Liquid electrolyte [ consisting of LiPF6Dissolved in Ethylene Carbonate (EC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC) in a volume ratio of 1:1:1, LiPF6Concentration 1M) from Dry Chemicals, Suzhou.
Example 1
The following provides a LiAl5O8The preparation method of the nanowire film is shown in figure 1, and the specific preparation method comprises the following steps:
(1) preparation of Al (EtO)3Nanowire gel: al (EtO)3Nanowire gels can be prepared as referenced to d.lei, j.benson, a.magasinski, g.berdichevsky, g.yushi, Science 2017,355,267. Specifically, a graphite crucible containing aluminum powder (0.3g) and a Li block (0.085g) (1:1 atomic ratio) was placed in a muffle furnace, heated at 800 ℃ for 30min, and naturally cooled to obtain a Li-Al alloy sheet. The Li-Al alloy sheet was polished in a glove box filled with argon gas, and the polished Li-Al alloy sheet (0.1105g) was reacted with ethanol (20mL) at 60 ℃ for 30 hours to give Al (EtO)3Nanowire gels.
(2) Preparation of LiAl5O8Nanowire films: for Al (EtO)3The nanowire gel was suction filtered leaving a layer of Al (EtO) on the filter paper3The nanowire film is then naturally dried. Mixing the Al (EtO)3The nanowire film was placed in a muffle furnace at 1 ℃ min-1The heating rate of (2) is increased to 400 ℃ for precalcination for 10 min. Then 50mg of Al (EtO)3The nanowire films were soaked in 20mL of 0.15M EtOLi ethanol solution to supplement Li source to the films for 5 min. After the soaking, the nanowire film was taken out of the EtOLi solution, and then placed in a muffle furnace at 1 ℃ for min-1The temperature rise rate of (1) is from room temperature to 600 ℃, and then 5 ℃ min-1Raising the temperature to 1150 ℃, preserving the temperature for 2 hours, and naturally cooling to obtain LiAl5O8A nanowire film. In this step, the precalcination and calcination steps in the muffle furnace were carried out in air, and the other operations were carried out in a glove box filled with argon.
The LiAl5O8The XRD spectrum and SEM images of the nanowire films are shown in fig. 2 and 3, respectively. The XRD pattern is except LiAl5O8Has no impurity peak outside the characteristic diffraction peak, which indicates that high-purity impurity-free LiAl is successfully prepared5O8. From the SEM image, the LiAl can be seen5O8Has the shape of a nanowire.
Comparative example 1
This comparative example differs from example 1 in that: mixing Al (EtO)3After the nanowire gel was suction filtered to form a film, the nanowire film was washed three times with ethanol (10ml) to remove all EtOLi (preparation Al (EtO))3Etoli) formed during nanowire gelation, then directly heated to 1200 deg.C to obtain alpha-Al2O3A nanowire film.
Specifically, for Al (EtO)3The nanowire gel was suction filtered leaving a layer of Al (EtO) on the filter paper3The nanowire film was then washed three times with ethanol (10ml) to remove all the EtOLi, and then dried naturally. Mixing the Al (EtO)3The nanowire film was placed in a muffle furnace at 1 ℃ min-1The temperature rise rate of (1) is from room temperature to 600 ℃, and then 5 ℃ min-1Raising the temperature to 1200 ℃, preserving the temperature for 2 hours, and then naturally cooling to obtain alpha-Al2O3A nanowire film.
(1) Preparation of composite solid electrolyte
PVDF-HFP (0.96g) was dissolved in ethanol (0.48g) and acetone (8.64g), and stirred at 50 ℃ for 2 hours to prepare a PVDF-HFP solution. Will be 40mg LiAl of example 15O8The nanowire film was immersed in 9.3g of PVDF-HFP solution for 3 min. After the impregnation is finished, LiAl is added5O8And taking out the nanowire film, and naturally drying to obtain the LPH film. The LPH membrane was cut into a disk having a diameter of 14mm (thickness: about 100 μ M), and the disk was immersed in 5g of an electrolyte (1M LiPF)6in EC, DMC, EMC 1:1:1 Vol%) for 12h, so that the LPH film can fully absorb the electrolyte. After soaking, the excess electrolyte is drained to obtain a composite solid electrolyte, which is marked as LPH-GPE and 27 mu L of electrolyte is absorbed by LPH-GPE.
The same method was used to subject the α -Al of comparative example 1 to2O3The nanowire film was immersed in PVDF-HFP solution to prepare a comparative APH-GPE absorbed with 27. mu.L of electrolyte.
(2) Assembled battery
Assembling LPH-GPE and APH-GPE into a Cu/Li battery or an LFP/Li battery, wherein the method comprises the following steps:
LFP (70 wt.%), acetylene black (20 wt.%), polyvinylidene fluoride (10 wt.%) were dissolved in n-methyl-2-pyrrolidone (NMP) to form a slurry. And (3) coating the slurry on an aluminum foil, drying for 12h at 80 ℃, and cutting into LFP pole pieces with the diameter of 10 mm. And assembling the LFP pole piece, the LPH-GPE and the Li cathode into a 2032 type button cell in a glove box, and marking the button cell as an LFP/LPH-GPE/Li battery. And assembling the Cu foil, the LPH-GPE and the Li cathode into a Cu/LPH-GPE/Li battery in a glove box.
And assembling the LFP pole piece, the APH-GPE and the Li cathode into an LFP/APH-GPE/Li battery by adopting the same method, and assembling the Cu foil, the APH-GPE and the Li cathode into a Cu/APH-GPE/Li battery in a glove box.
In Cu/LPH-GPE/Li battery and Cu/APH-GPE/Li battery, respectively, at 0.5mA cm-2The current density of (a) causes Li to be deposited on the surface of the Cu foil, and the morphology of Li deposited on the Cu foil is shown in fig. 4. As can be seen from fig. 4, with LPH-GPE, Li is deposited in two dimensions, forming a layered Li metal, avoiding the risk of short circuits due to penetration of the electrolyte. This is because LiAl5O8The nanowires will reduce to produce an Al layer upon the application of lithium. Al is uniformly distributed in LiAl5O8The edges of the nanowires, which not only promote the formation of uniform nucleation sites, but also homogenizeLi+Flow of Li thereby+Deposited in a flake form rather than a dendritic form. When APH-GPE is used, sharp Li dendrites are formed on the Li deposition layer, and the side reaction of the electrode and the electrolyte is greatly increased.
In the LFP/LPH-GPE/Li battery and the LFP/APH-GPE/Li battery, 1C (1C 170mA · g) was used, respectively-1) After the current density is charged and discharged for 50 times, the LFP/LPH-GPE/Li battery is uniformly distributed with a smooth and compact SEI film on the Li cathode; in the LFP/APH-GPE/Li battery, however, the SEI film is thick due to lithium dendrites and severe cracks occur, as shown in FIG. 5.
And applying 1C (1C is 170 mA-g) to the LFP/LPH-GPE/Li battery and the LFP/APH-GPE/Li battery within a voltage window of 2.5-3.8V-1) Constant current charging and discharging are carried out. As shown in FIG. 6, the initial specific capacities of the LFP/LPH-GPE/Li battery and the LFP/APH-GPE/Li battery were 139.6 mAh g, respectively-1And 140.4mAh · g-1. After 150 cycles, the specific capacity of the LFP/LPH-GPE/Li battery is 144mAh g-1No decay occurred, while the specific capacity decay of LFP/LPH-GPE/Li battery was 133.9mAh g-1It is stated that LPH-GPE can improve long-term cyclability of the battery because the dendrite-free lithium negative electrode and the high-quality SEI film are Li in LFP/LPH-GPE/Li battery+Fast and uniform migration at the interface of lithium metal and solid electrolyte provides a good environment.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. LiAl5O8The preparation method of the nanowire is characterized by comprising the following steps: the method comprises the following steps:
for Al (EtO)3Pre-calcining the nanowires, and then putting the pre-calcined Al (EtO) in a protective atmosphere3Soaking the nano-wire in a lithium ion solution;
after the soaking, solid-liquid separation is carried out to obtain Al (EtO) for supplementing lithium3A nanowire;
calcining the lithium-supplemented Al (EtO)3Nanowire to obtain LiAl5O8A nanowire.
2. The LiAl of claim 15O8The preparation method of the nanowire is characterized by comprising the following steps: the lithium ion solution comprises at least one of a lithium ethoxide solution, a lithium phosphate solution, a lithium perchlorate solution, a lithium carbonate solution and a lithium methoxide solution.
3. The LiAl of claim 15O8The preparation method of the nanowire is characterized by comprising the following steps: the pre-calcining temperature is 300-500 ℃.
4. The LiAl of claim 15O8The preparation method of the nanowire is characterized by comprising the following steps: the calcining temperature is 800-1500 ℃.
5. The LiAl of claim 45O8The preparation method of the nanowire is characterized by comprising the following steps: the calcination is specifically carried out at 0.5-1.5 ℃ per min-1The temperature rise rate is from room temperature to 500-600 ℃, and then 4-6 ℃ per minute-1Raising the temperature to 800-1500 ℃, preserving the heat for 1-4 h, and then naturally cooling.
6. A composite solid electrolyte characterized by: the composite solid electrolyte contains LiAl5O8Nanowire of said LiAl5O8The nanowires are prepared by the preparation method of any one of claims 1 to 5.
7. The composite solid electrolyte of claim 6, wherein: the composite solid electrolyte contains LiAl5O8Nanowires and a conductive gel polymer encapsulating the LiAl5O8A nanowire.
8. The composite solid electrolyte of claim 7, wherein: the composite solid electrolyte also contains lithium salt, and the lithium salt is dispersed in the LiAl5O8Nanowires and conductive gel polymers.
9. A preparation method of a composite solid electrolyte is characterized by comprising the following steps: the method comprises the following steps: mixing LiAl5O8Soaking the nano-wire in a conductive gel polymer solution, and drying to obtain a conductive gel polymer coated LiAl5O8A film of nanowires a; allowing the film a to absorb a lithium salt solution to obtain a composite solid electrolyte; the LiAl5O8The nanowires are prepared by the preparation method of any one of claims 1 to 5.
10. A lithium metal battery, characterized in that: the lithium metal battery comprises the composite solid electrolyte according to any one of claims 6 to 8.
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