CN112242519B - Positive electrode material, preparation method thereof and solid-state lithium battery - Google Patents
Positive electrode material, preparation method thereof and solid-state lithium battery Download PDFInfo
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Abstract
The invention provides a positive electrode material which is in a core-shell structure, wherein the core is a positive electrode active substance, and the shell comprises lithium-containing transition metal oxide and Ti 2 O 3 Said lithium-containing transition metal oxide having an ionic conductivity of greater than 10 ‑8 S·cm ‑1 The lithium-containing transition metal oxide can be delithiated to form an oxide at a voltage of more than 3.0V, and the electronic conductivity of the oxide is more than 10 ‑6 S·cm ‑1 . The invention also provides a preparation method of the cathode material and a solid-state lithium battery. The positive electrode material can simultaneously construct a lithium ion transmission channel and an electron transmission channel, and greatly improves the capacity exertion, the first-turn coulomb efficiency, the cycle performance and the high-rate performance of the solid-state lithium battery.
Description
Technical Field
The invention relates to the technical field of lithium ion battery anode materials, in particular to an anode material, a preparation method thereof and a solid-state lithium battery.
Background
The lithium battery has the advantages of high energy density, good cycle performance and the like and is widely applied, however, as the liquid organic solvent is used as the electrolyte, the leakage, the air blowing, the fire and the like of the battery can be caused, and the serious potential safety hazard is brought to a battery system. The solid-state lithium battery adopts solid electrolyte to replace organic liquid electrolyte used in the existing battery, thereby greatly improving the safety performance of the battery.
In the solid-state lithium battery in the prior art, a side reaction between the positive active material and the solid electrolyte exists, and the occurrence of the side reaction can cause the reduction of the battery performance and the attenuation of the battery capacity. Therefore, the positive electrode material is usually subjected to a surface coating treatment for isolating the contact between the positive electrode active material and the solid electrolyte, thereby suppressing the occurrence of side reactions therebetween. Wherein the coating material can be oxide, lithium-containing transition metal oxide, such as LiNbO 3 、LiTaO 3 、Li 4 Ti 5 O 12 、Al 2 O 3 Etc., wherein LiNbO is used 3 Coated positive electrode materials are most widely used. However, coating with such substances is only to improve the positive electrode activityThe compatibility of the solid electrolyte with the active material is aimed at reducing the risk and probability of oxidation of the solid electrolyte by the active material of the positive electrode, so that the effect of the coating on the interface optimization is limited; moreover, the coating with such substances also severely reduces the electronic conductance of the positive active material, resulting in poor performance of the assembled solid-state lithium battery and limited improvement of the battery performance.
Disclosure of Invention
In order to solve the technical problems that the electron conductivity of a positive electrode material is reduced and the performance of a solid-state lithium battery is poor after the positive electrode active material is coated in the prior art, the invention provides the positive electrode material, a preparation method of the positive electrode material and the solid-state lithium battery.
In order to achieve the above object, in a first aspect, the present invention provides a positive electrode material having a core-shell structure, the core being a positive electrode active material, and the shell including a lithium-containing transition metal oxide and Ti 2 O 3 The lithium-containing transition metal oxide has an ionic conductivity of more than 10 -8 S·cm -1 The lithium-containing transition metal oxide can be delithiated to generate oxide at a voltage higher than 3.0V, and the electronic conductivity of the oxide is higher than 10 -6 S·cm -1 。
Compared with the prior art, the lithium-containing transition metal oxide and Ti in the anode material provided by the invention 2 O 3 The lithium-containing transition metal oxide can be removed from lithium under high pressure to generate an oxide product with electron conductivity, so that the cathode material can have both electron conductivity and ion conductivity. And Ti in the clad layer 2 O 3 The valence changes in the process of lithium removal of the lithium-containing transition metal oxide, thereby providing electrons to support the reaction of lithium removal of the lithium-containing transition metal oxide and conversion of the lithium-containing transition metal oxide into the corresponding oxide, namely, the function of supporting the continuous progress of the redox reaction is realized. Is justBecause of the lithium-containing transition metal oxide and Ti 2 O 3 When the positive electrode material is used as a positive electrode of a lithium battery, after the battery is charged and discharged for the first time, partial lithium-containing transition metal oxide in the positive electrode material can perform in-situ delithiation reaction to obtain corresponding oxides, the oxides have high electronic conductivity, and the lithium-containing transition metal oxide per se has high lithium ion conductivity, so that after charging, the positive electrode material can have high electronic conductivity and ion conductivity at the same time, a lithium ion transmission channel and an electron transmission channel can be simultaneously constructed in the battery, the battery performance is improved, and the capacity exertion, the first-turn coulomb efficiency, the cycle performance and the high-rate performance of the lithium battery are improved.
In a second aspect, the present invention provides a method for preparing a positive electrode material, comprising the steps of:
(1) Mixing the positive electrode active material, lithium-containing transition metal oxide and Ti 2 O 3 Carrying out ball milling reaction together;
(2) Carrying out heat treatment on the reaction product obtained in the step (1) at a certain temperature to obtain a positive electrode material;
the positive electrode material is of a core-shell structure, the core is a positive electrode active substance, and the shell comprises lithium-containing transition metal oxide and Ti 2 O 3 The lithium-containing transition metal oxide has an ionic conductivity of more than 10 -8 S·cm -1 The lithium-containing transition metal oxide can be delithiated to form an oxide at a voltage of more than 3.0V, and the electronic conductivity of the oxide is more than 10 -6 S·cm -1 。
Compared with the prior art, the method provided by the invention can be used for preparing the cathode material with the core-shell structure, and the shell comprises the lithium-containing transition metal oxide, so that the cathode material has high lithium ion transmission performance, and the interface with the solid electrolyte can be optimized, so that the interface impedance is reduced; the shell also contains Ti 2 O 3 Which reacts with a lithium-containing transition metal oxide at a high voltage to produce an oxide product, and which is a semiconductor having excellent electron conductivity,so that the positive electrode material has the function of automatically generating a new electronic path after being charged. Therefore, when the cathode material obtained by the method provided by the invention is used in a lithium battery, the capacity exertion, the first-turn coulombic efficiency, the cycle performance and the high rate performance of the battery can be obviously improved.
In a third aspect, the invention further provides a solid-state lithium battery, which includes the above-mentioned cathode material or the cathode material prepared by the above-mentioned preparation method.
Because the anode material adopted in the solid lithium battery is of a core-shell structure, the existence of the shell can prevent the anode active substance from contacting with the solid electrolyte, thereby effectively avoiding the occurrence of side reaction between the anode active substance and the solid electrolyte and prolonging the cycle life of the battery. In addition, the shell contains lithium-containing transition metal oxide and Ti 2 O 3 So that the cathode material has high ionic conductivity and electronic conductivity; after the battery is charged, partial transition metal oxide can be delithiated to generate oxide, and the oxide has high electronic conductivity, so that the transmission of electrons in the battery circulation can be improved, and an electron transmission channel is constructed in the battery. Because the solid-state lithium battery contains the anode material, an electron transmission path and an ion transmission path can be simultaneously constructed in the battery during the battery cycle, and the capacity exertion, the first-turn coulomb efficiency, the cycle performance and the high-rate performance of the battery are greatly improved.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In a first aspect, the present invention provides a positive electrode material having a core-shell structure, wherein the core is a positive electrode active material, and the shell comprises a lithium-containing transition metal oxide and Ti 2 O 3 The lithium-containing transition metal oxide has an ionic conductivity of more than 10 -8 S·cm -1 The lithium-containing transition metal oxide can be delithiated to form oxide at voltage higher than 3.0V, and the electronic conductivity of the oxide is higher than 10 -6 S·cm -1 。
The prior art also uses lithium-containing transition metal oxides, such as LiNbO, for coating the positive electrode active material 3 、LiTaO 3 、Li 4 Ti 5 O 12 However, the cathode materials coated with these lithium-containing transition metal oxides have poor electron conductivity, i.e., inhibit electron transport during battery cycling, thereby affecting the performance of the battery. The lithium-containing transition metal oxide adopted by the invention is different from LiNbO 3 、LiTaO 3 、Li 4 Ti 5 O 12 The coated positive electrode material has excellent ion conduction performance, and the oxide product with excellent electron conduction performance can be obtained by oxidizing and delithiating under high voltage, so that the coated positive electrode material has the performance of ion conduction and electron conduction. Furthermore, the coating layer of the cathode material provided by the invention also contains Ti 2 O 3 ，Ti 2 O 3 The existence of the lithium-containing transition metal oxide can help the lithium-containing transition metal oxide to smoothly remove lithium under high voltage to obtain a product with electron conduction performance, thereby improving the performance of the coated anode material.
Further, the lithium-containing transition metal oxide is selected from LiCrO 2 、LiPrO 2 、Li 2 MoO 3 One or more of them.
LiCrO 2 、LiPrO 2 And Li 2 MoO 3 The lithium-ion-conducting lithium-ion battery cathode material has good ion conductivity, can remove lithium under high pressure to generate a semiconductor oxide product, and has excellent electron conductivity, so that the electron conductivity of the cathode material can be improved, the cathode material has the performance of electron transmission and ion transmission, and the battery performance is improved.
Further, ti 2 O 3 The mass ratio of the shell is 2-25%.
Ti 2 O 3 The function of the shell layer is to support lithium-containing transition metal oxide (with good ionic conductivity) in the shell layer to carry out delithiation to generate corresponding product with electron conductivityThus, ti is selected within this mass ratio range 2 O 3 The proportion of the lithium-containing transition metal oxide to the corresponding transition metal oxide can be balanced as much as possible, namely the proportion of the ion conducting substance and the electron conducting substance in the positive electrode material is balanced, so that the aim of optimizing the performance of the battery can be fulfilled.
Further, the mass proportion of the shell in the positive electrode material is 0.1-20%.
The mass ratio in this range not only optimizes the interface between the positive electrode material and the electrolyte, reduces the interface impedance, but also maintains the energy density of the positive electrode active material.
Further, the thickness of the shell is 10nm to 5 μm.
The thickness of the shell in the range not only can optimize the interface of the anode material and the electrolyte and reduce the interface impedance, but also can maintain the energy density of the anode material; when the thickness of the shell is thick, the electron conductivity of the positive electrode material is reduced, and the energy density of the whole battery is also reduced; when the thickness of the shell is small, the optimal interface between the positive electrode and the electrolyte cannot be maintained.
Furthermore, after the battery is charged by the positive electrode material, the shell also comprises oxide and TiO 2 The oxide is obtained by in-situ delithiation conversion of lithium-containing transition metal oxide, tiO 2 Is made of Ti 2 O 3 Obtained by in-situ conversion.
That is, after the battery is charged, lithium in the positive electrode material is extracted, so the lithium-containing transition metal oxide in the shell is extracted to generate the corresponding oxide, and when the battery is discharged and lithium ions return to the positive electrode, the oxide does not obtain lithium to generate the lithium-containing transition metal oxide, that is, after the battery is charged for the first time, the oxide generated in the positive electrode material is stably stored in the positive electrode material. On the other hand, when the battery is charged, the positive electrode voltage is high, so that Ti in the positive electrode material 2 O 3 Oxidation to obtain TiO 2 When the battery is discharged again and lithium ions return to the positive electrode, lithium ions are received and lithium titanate (Li) is generated 2 TiO 3 ) The generated lithium titanate can be used as a positive electrode active substance to be present in a positive electrode materialThereby improving the capacity of the battery.
In addition, it is difficult to artificially prepare a positive electrode material having both an ion transport path and an electron transport path, and even if a material for lithium ion transport and electron transport is coated, it is incompatible with a solid electrolyte and a conductive agent, that is, a positive electrode active material cannot normally exert its capacity. And the in-situ generation can generate an oxide semiconductor product with excellent electronic conductivity by self-selection of the battery under the condition of keeping the ion channel unblocked, and a new electronic channel is established by self-selection, so that the whole composite positive electrode layer is optimized, and the performance of the battery is better improved.
Furthermore, after the battery is charged by the positive electrode material, the shell also comprises oxide and TiO 2 The oxide is Cr 2 O 3 、Pr 2 O 3 、MoO 2 One or more of them.
Oxide (Cr) 2 O 3 、Pr 2 O 3 、MoO 2 ) Has higher electron conductivity, thereby increasing the capability of the anode material for conducting electrons, and enabling an electron transmission channel to be constructed in the battery. In addition, the oxide is generated in situ by lithium-containing transition metal oxide, namely an electron transmission channel is constructed in situ on the ion transmission channel, so that lithium ions in the battery and a network for electron transmission are obviously optimized, and the comprehensive performance of the battery, such as cycle performance, capacity exertion, high rate performance and the like, is improved.
Further, 1% to 40% of the lithium-containing transition metal oxide is delithiated and converted into the transition metal oxide, and 2% to 100% of the Ti 2 O 3 Conversion to obtain TiO 2 。
The lithium-containing transition metal oxide has ion transmission performance, and the oxide generated in situ has electron transmission performance, so that partial conversion is realized, the positive electrode material can have the ion transmission performance and the electron transmission performance at the same time, an ion transmission channel and an electron transmission channel can be constructed in the battery at the same time, and the battery performance is improved.
Further, the positive electrode active material is selected from LiCoO 2 、LiNiO 2 、LiCo x Ni 1-x O 2 （0≤x≤1）、LiCo x Ni 1-x- y Al y O 2 （0≤x≤1，0≤y≤1）、LiMn 2 O 4 、LiFe x Mn y M z O 4 (M is at least one of Al, mg, ga, cr, co, ni, cu, zn or Mo, x is more than or equal to 0 and less than or equal to 1,0 and less than or equal to y is more than or equal to 1,0 and less than or equal to z is less than or equal to 1, x + y + z = 1), li 1＋x L 1－y－z M y N z O2 (L, M, N is at least one of Li, co, mn, ni, fe, al, mg, ga, ti, cr, cu, zn, mo, F, I, S, B, -0.1-0.2,0-1,0-1,0-y + z-1), liFePO 4 、Li 3 V 2 (PO 4 ) 3 、Li 3 V 3 (PO 4 ) 3 、LiVPO 4 F、Li 2 CuO 2 、Li 5 FeO 4 One or more of metal sulfide and metal oxide.
Further, the metal sulfide is TiS 2 、V 2 S 3 、FeS、FeS 2 、LiMS x (M is at least one of transition metal elements such as Ti, fe, ni, cu, mo and the like, and x is more than or equal to 1 and less than or equal to 2.5).
Further, the metal oxide is TiO 2 、Cr 3 O 8 、V 2 O 5 、MnO 2 One or more of them.
Further, the particle diameter of the positive electrode active material is 100nm to 500 μm.
In a second aspect, the present invention provides a method for preparing a positive electrode material, comprising the steps of:
(1) Mixing positive electrode active material, lithium-containing transition metal oxide and Ti 2 O 3 Putting the mixture into a high-energy ball milling tank together, and performing ball milling reaction under the condition of isolating air by using ethanol as a solvent;
(2) Carrying out heat treatment on the reaction product obtained in the step (1) at a certain temperature to obtain a positive electrode material;
wherein, theThe positive electrode material is of a core-shell structure, the core is a positive electrode active substance, and the shell comprises lithium-containing transition metal oxide and Ti 2 O 3 The lithium-containing transition metal oxide has an ionic conductivity of more than 10 -8 S·cm -1 The lithium-containing transition metal oxide can be delithiated to form an oxide at a voltage of more than 3.0V, and the electronic conductivity of the oxide is more than 10 -6 S·cm -1 。
The cathode material prepared by the method has excellent ion transmission, and during charging, the cathode material can generate substances with excellent electron transmission, so that an ion transmission channel and an electron transmission channel can be simultaneously constructed in the battery, and the performance of the battery is improved.
Further, the ball milling speed in the step (1) is 300rpm, and the ball milling time is 20h.
Further, the heat treatment in the step (2) comprises the steps of drying at the temperature of 100-180 ℃ in vacuum drying, and then placing in a muffle furnace for high-temperature treatment at the temperature of 400-1000 ℃ and keeping for 8-24 hours.
In a third aspect, the invention provides a solid-state battery, which comprises the positive electrode material or the positive electrode material prepared by the preparation method.
The cathode material used by the solid-state battery has excellent ion conductivity, and can improve the electron conductivity after being charged, thereby being beneficial to constructing an ion transmission channel and a battery transmission channel in the battery and improving the battery performance.
Furthermore, after the solid lithium battery is charged, the shell of the positive electrode material also comprises oxide and TiO 2 The oxide is obtained by lithium removal conversion of lithium-containing transition metal oxide.
Further, the solid electrolyte adopted by the solid lithium battery is one or more of NASICON type solid electrolyte, perovskite type solid electrolyte, sulfur type solid electrolyte and garnet type solid electrolyte.
Further, the NASICON type solid electrolyte is selected from LiM 2 (PO 4 ) 3 LiM containing doping element 2 (PO 4 ) 3 Wherein M is one or more selected from Ti, zr, ge, sn and Pb, and the doping element is one or more selected from Mg, ca, sr, ba, sc, al, ga, in, nb, ta and V.
Further, the chemical formula of the perovskite type solid electrolyte is A x B y TiO 3 、A x B y Ta 2 O 6 、A x B y Nb 2 O 6 、A h M k D n Ti w O 3 Wherein x +3y =2, h +2k +5n +4w =6,0 < x < 2,0 < y < 2/3,h, k, n, w are all greater than 0; a is at least one of Li and Na elements, B is at least one of La, ce, pr, Y, sc, nd, sm, eu and Gd elements, M is at least one of Sr, ca, ba, ir and Pt elements, and D is at least one of Nb and Ta elements.
Further, the sulfur-based solid electrolyte is selected from crystalline Li x M y P z S w (M is one or more of Si, ge and Sn, wherein x +4y +5z =2w, y is more than or equal to 0 and less than or equal to 1.5) and glassy Li 2 S-P 2 S 5 (including Li) 7 P 3 S 11 、70Li 2 S-30P 2 S 5 Etc.), glass-ceramic state Li 2 S-P 2 S 5 Li containing doping element 2 S-P 2 S 5 Wherein the doping element is one or more of O, cl and I.
Further, the garnet-type solid electrolyte is specifically Li 7+a-b-3c Al c La 3-a X a Zr 2-b Y b O 12 (ii) a Wherein a is more than 0 and less than or equal to 1,0 and more than or equal to b is more than or equal to 1,0 and more than c is more than or equal to 1,X is one or more of La, ca, sr, ba and K, and Y is one or more of Ta, nb, W and Hf.
Further, the particle diameter of the solid electrolyte is preferably in the range of 1nm to 5 μm.
In the case where the particle size is within this range, the interface between the positive electrode material and the solid electrolyte can be optimized, and if the particle size is too large, the transport of lithium ions is not facilitated, and the energy density of the battery can be reduced, and if the particle size is too small, the interface can hardly be optimized.
The negative electrode active material used in the solid-state lithium battery is a negative electrode active material capable of intercalating and deintercalating lithium, which is commonly used by those skilled in the art, and may be selected from one or more of carbon materials, tin alloys, silicon, tin, and germanium, and metallic lithium, lithium-indium alloys, and the like may be used. The carbon material may be non-graphitized carbon, graphite, or carbon obtained by high-temperature oxidation of polyacetylene polymer material, or one or more of pyrolytic carbon, coke, organic polymer sinter, and activated carbon.
Further, the preparation method of the solid-state lithium battery is also a commonly used process method in the field, and specifically comprises the following steps:
coating the selected positive electrode material layer (C) on the positive electrode current collector, then coating a solid electrolyte layer (E) on the surface of the positive electrode material layer, and laminating the negative electrode active material layer (A) coated on the negative electrode current collector and the CE layer together to form the solid lithium battery (CEA).
The positive electrode material layer comprises a positive electrode active substance compositely coated by transition metal sulfide and corresponding transition metal oxide, a conductive agent, a binder and the like, and can be prepared by the existing preparation method:
coating slurry containing a positive active substance compositely coated by a transition metal sulfide and a corresponding transition metal oxide, an electrode adhesive and a solvent on a positive current collector, drying, forming a positive material layer on the positive current collector, and then performing rolling treatment at 0-5 MPa to obtain a positive material layer (C). Wherein, the binder is a cathode binder commonly used in the field, and can be one or more of fluorine-containing resin and polyolefin compound, such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE) and Styrene Butadiene Rubber (SBR). The conductive agent is a positive electrode conductive agent commonly used in the field, and can be acetylene black, carbon nanotubes, carbon fibers, carbon black and the like. The content of the binder is 0.01 to 10wt%, preferably 0.02 to 5wt%, based on the weight of the positive electrode material; the content of the conductive agent is 0.1 to 20wt%, preferably 1 to 10wt%. Wherein, the solvent can be one or more selected from N-methylpyrrolidone (NMP), water, ethanol and acetone, and the dosage of the solvent is generally 50-400wt%.
Wherein the solid electrolyte layer (E) contains a solid electrolyte and a binder. The solid electrolyte layer (E) is produced by a coating method:
and (3) coating the slurry containing the solid electrolyte, the adhesive and the solvent on the surface of the positive electrode material layer (C), drying and rolling to form the CE. Wherein, the binder is selected from one or more of polythiophene, polypyrrole, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polystyrene, polyacrylamide, ethylene-propylene-diene copolymer resin, styrene butadiene rubber, polybutadiene, fluororubber, polyethylene oxide, polyvinylpyrrolidone, polyester resin, acrylic resin, phenolic resin, epoxy resin, polyvinyl alcohol, carboxypropyl cellulose, ethyl cellulose, polyethylene oxide, sodium carboxymethylcellulose (CMC) and styrene butadiene latex (SBR). The solvent is selected from one or more of water, ethanol, toluene, N-methyl pyrrolidone and common lipids.
Among them, the components of the anode active material layer (a) are commonly used in the art, and include an anode active material and a binder. The adopted negative electrode active material is various negative electrode active materials which can insert and remove lithium and are commonly used in the field; the binder is various negative electrode binders commonly used in the art, and may be, for example, one or more selected from polythiophene, polypyrrole, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polystyrene, polyacrylamide, ethylene-propylene-diene copolymer resin, styrene butadiene rubber, polybutadiene, fluororubber, polyethylene oxide, polyvinylpyrrolidone, polyester resin, acrylic resin, phenol resin, epoxy resin, polyvinyl alcohol, carboxypropyl cellulose, ethyl cellulose, sodium carboxymethylcellulose (CMC), and styrene butadiene latex (SBR). Preferably, the binder is contained in the anode active material layer (a) in an amount of 0.01 to 10wt% based on the weight of the anode active material. The negative active material layer (A) is obtained by mixing a negative active material, a binder and the like in a solvent according to a certain proportion, uniformly stirring to obtain the required negative slurry, then coating the slurry on a negative current collector, and drying and tabletting to obtain the negative active material layer (A). When lithium or lithium-indium alloy is used for the negative electrode, metallic lithium ribbon or lithium-indium alloy ribbon can be directly used.
And finally, pressing the A and the CE together to form the CEA, thus obtaining the solid lithium battery, wherein the pressing mode is preferably isostatic pressing.
The present invention is further illustrated by the following specific examples, which are provided only for illustrating and explaining the present invention and are not intended to limit the present invention.
Example 1
(1) Production of Positive electrode Material layer (C)
Preparing a positive electrode material with a core-shell structure: under inert gas conditions, 1000g of LiCoO 2 (particle size about 5 μm) with 18g Li 2 MoO 3 And 2g of Ti 2 O 3 Putting the materials into a high-energy ball milling tank together, adding 500 mL ethanol solution, and performing high-energy ball milling after completely sealing, wherein the ball milling speed is 300rpm, and the ball milling time is 20h. And then, transferring the obtained product to a vacuum drying oven for vacuum drying at the temperature of 100 ℃ until the product is completely dried, taking out the product, putting the product into a muffle furnace, heating the product to 400 ℃ for 8h to obtain the core-shell structure cathode material, wherein the thickness of the shell is about 65nm.
Subsequently, 930 g of the above-obtained positive electrode material, 150 g of Li 10 GeP 2 S 12 30 g binder PVDF, 20g acetylene black, 20g conductive agent carbon fiber were added to 1500 g solvent NMP (nitrogen methyl pyrrolidone), and then stirred in a vacuum stirrer to form stable and uniform positive electrode slurry. The positive electrode slurry was uniformly coated intermittently on both sides of an aluminum foil (aluminum foil size: width 160 mm, thickness 16 μm), and then 393K was dried, and was pressed into sheets by a roll press to obtain C.
(2) Fabrication of positive electrode material layer and solid electrolyte layer (CE)
In a glove box, 600 g Li was mixed 10 GeP 2 S 12 Placing into 1200 g toluene solutionThe solution contains 30 g butadiene rubber binder, and then is heated and stirred to a stable and uniform solution. The solution was continuously coated on the C obtained in step (1), and then 333K was dried and cut into CEs of dimensions 485 mm (length) × 46 mm (width).
(3) Production of negative electrode active Material layer (A)
940 g negative active material artificial graphite, 30 g binder CMC and 30 g binder SBR were added to 1200 g deionized water, and then stirred in a vacuum stirrer to form stable and uniform negative electrode slurry. The slurry was uniformly coated intermittently on both sides of a copper foil (copper foil size: width 160 mm, thickness 16 μm), then 393K was dried, and after being rolled by a roll press, negative electrode sheets having size 480 mm (length) × 45 mm (width) were cut out.
(4) Preparation of CEA
And (3) in a glove box, aligning the CE obtained in the step (2) and the A obtained in the step (3) after cutting, placing the CE and the A in a hot press, carrying out 423K hot pressing on 1 h, vacuumizing and sealing by using an aluminum plastic film, and taking out a sample.
The pressed sample is pressed in an isostatic press under the condition of 200 MPa and 300 s to obtain the battery of the embodiment.
Example 2
The same procedure as in example 1 was used to prepare a positive electrode material and a solid lithium battery of this example, except that:
in the step (1), 2.2 g TiCl is adopted when preparing the cathode material with the core-shell structure 3 Due to TiCl 3 Hydrolysis will generate Ti in situ 2 O 3 So that Li in the shell in the obtained positive electrode material 2 MoO 3 With Ti 2 O 3 Mixing at the nanometer level can be achieved, with a shell thickness of 65nm.
Example 3
The same procedure as in example 1 was used to prepare a positive electrode material and a solid lithium battery of this example, except that:
in the step (1), when the anode material with the core-shell structure is prepared, 16g of LiCoO is adopted 2 And 4 g Ti 2 O 3 And the rest steps and operations are unchanged, wherein the thickness of the shell is 65nm.
Example 4
The same procedure as in example 1 was used to prepare a positive electrode material and a solid lithium battery of this example, except that:
in the step (1), when the anode material with the core-shell structure is prepared, 9gLi is adopted 2 MoO 3 、9gLiCrO 2 And 2gTi 2 O 3 And the rest steps and operations are unchanged, wherein the thickness of the shell is 65nm.
Example 5
The same procedure as in example 1 was used to prepare a positive electrode material and a solid lithium battery of this example, except that:
in the step (1), when preparing the cathode material with the core-shell structure, 6g of Li is adopted 2 MoO 3 、6g LiCrO 2 、6g LiPrO 2 And 2g TiCl 3 And the rest steps and operations are unchanged, wherein the thickness of the shell is 65nm.
Example 6
The same procedure as in example 1 was used to prepare a positive electrode material and a solid lithium battery of this example, except that:
in the step (1), when the anode material with the core-shell structure is prepared, 0.9gLi is adopted 2 MoO 3 And 0.1g Ti 2 O 3 And the rest steps and operations are unchanged, wherein the thickness of the shell is 5nm.
Example 7
The same procedure as in example 1 was used to prepare a positive electrode material and a solid lithium battery of this example, except that:
in the step (1), 180gLi is adopted when the anode material with the core-shell structure is prepared 2 MoO 3 And 20g of Ti 2 O 3 And the rest steps and operations are unchanged, wherein the thickness of the shell is 700nm.
Comparative example 1
A solid lithium battery of this comparative example was prepared by the same procedure as in example 1, except that:
the positive electrode usedThe material is uncoated LiCoO 2 And then directly using the positive active material to assemble the solid lithium battery, and keeping the rest steps and operation unchanged.
Comparative example 2
A solid lithium battery of this comparative example was prepared by the same procedure as in example 1, except that:
the used anode material is LiNbO 3 Coated LiCoO 2 The material is LiNbO with the coating amount of 3 percent by mass 3 Coated LiCoO 2 Coating method 1000g LiCoO 2 Fully mixing 51mL of niobium ethoxide, 12g of lithium ethoxide, 1000mL of deionized water and 1000mL of ethanol, then dropwise adding ammonia water to the pH value of 10 under continuous stirring, evaporating the solution to dryness, and heating the obtained powder at 400 ℃ for 8 hours to obtain LiNbO 3 Coated LiCoO 2 And then directly using the cathode material to assemble the solid-state lithium battery, and keeping the rest steps and operation unchanged, wherein the thickness of the shell is 55nm.
Comparative example 3
A solid lithium battery of this comparative example was prepared by the same procedure as in example 1, except that:
in the step (1), when the anode material with the core-shell structure is prepared, 300gLi is adopted 2 MoO 3 And 33g TiCl 3 And the rest steps and operations are unchanged, wherein the thickness of the shell is 1 mu m.
Comparative example 4
A solid lithium battery of this comparative example was prepared by the same procedure as in example 1, except that:
in the step (1), when preparing the cathode material with the core-shell structure, 16g of Li is adopted 2 MoO 3 ，1.3g MoO 2 ， 0.5 g Ti 2 O 3 And 1.67g TiO 2 And (4) coating, wherein the rest steps and operation are unchanged. The thickness of the shell is approximately 67nm.
Battery performance testing
The solid state lithium batteries obtained in examples 1 to 7 and comparative examples 1 to 4 were subjected to a cycle life test of the batteries according to the following method: the batteries prepared in the examples and the comparative examples are 20 batteries, and the batteries are subjected to charge and discharge cycle tests at different magnifications (0.1C, 1C, 5C) on a LAND CT 2001C secondary battery performance detection device under the condition of 298 +/-1K. The method comprises the following steps: standing for 10 min; constant voltage charging is carried out until 4.2V/0.05C is cut off; standing for 10 min; constant current discharge to 2.0V, i.e. 1 cycle. Repeating the steps, when the battery capacity is lower than 80% of the first discharge capacity in the circulation process, the circulation is terminated, the circulation times are the circulation service life of the battery, each group is averaged, and the parameters, the average first discharge capacity of the battery and the data of the average first circulation coulombic efficiency of the battery are shown in tables 1 and 2. As can be seen from tables 1 and 2, the lithium battery cathode material provided by the invention has higher first discharge specific capacity, higher first cycle coulombic efficiency, longer cycle life and better high rate performance when applied to an all-solid-state lithium battery. Among them, since the oxide used in comparative example 4 is not generated in situ from the lithium-containing transition metal oxide, the ion transport path and the electron transport path constructed inside the battery occupy a space with each other, causing a loss of a part of the transport path, and thus performing less well than the present invention in terms of battery performance.
TABLE 1
TABLE 2
Claims (13)
1. The positive electrode material is characterized by having a core-shell structure, wherein the core is a positive electrode active material, and the shell comprises a lithium-containing transition metal oxide and Ti 2 O 3 Said lithium-containing transition metal oxide having an ionic conductivity of greater than 10 -8 S·cm -1 The lithium-containing transition metal oxide can be delithiated to form an oxide at a voltage of more than 3.0V, and the electronic conductivity of the oxide is more than 10 -6 S·cm -1 ；
After the battery formed by the positive electrode material is charged, the shell also comprises oxide and TiO 2 The oxide is obtained by in-situ delithiation conversion of the lithium-containing transition metal oxide, and the TiO 2 Is made of the Ti 2 O 3 In-situ conversion is carried out to obtain;
from 1% to 40% of said lithium-containing transition metal oxide is delithiated to convert to said oxide.
2. The positive electrode material according to claim 1, wherein the lithium-containing transition metal oxide is selected from LiCrO 2 、LiPrO 2 、Li 2 MoO 3 One or more of them.
3. The positive electrode material as claimed in claim 1, wherein the Ti is 2 O 3 The mass of the shell is 2-25%.
4. The positive electrode material according to claim 1, wherein the mass ratio of the shell in the positive electrode material is 0.1 to 20%.
5. The positive electrode material according to claim 1, wherein the shell has a thickness of 10nm to 5 μm.
6. The positive electrode material as claimed in claim 2, wherein the shell further comprises an oxide and TiO after the positive electrode material is assembled into a battery and charged 2 The oxide is Cr 2 O 3 、Pr 2 O 3 、MoO 2 One or more of them.
7. The positive electrode material according to claim 6, wherein 2 to 100% of the Ti is contained 2 O 3 Into said TiO 2 。
8. The positive electrode material according to claim 1, wherein the positive electrode is activatedThe substance is selected from LiCoO 2 ，LiNiO 2 ，LiCo x Ni 1-x O 2 、0≤x≤1，LiCo x Ni 1-x-y Al y O 2 、0≤x≤1、0≤y≤1，LiMn 2 O 4 ，LiFe x Mn y M z O 4 M is at least one of Al, mg, ga, cr, co, ni, cu, zn or Mo, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and x + y + z =1 1＋ x L 1－y－z M y N z O 2 L, M, N is at least one of Li, co, mn, ni, fe, al, mg, ga, ti, cr, cu, zn, mo, F, I, S, B, -0.1-0.2, 0-1, y + z, liFePO 4 ，Li 3 V 2 (PO 4 ) 3 ，Li 3 V 3 (PO 4 ) 3 ，LiVPO 4 F，Li 2 CuO 2 ，Li 5 FeO 4 One or more of metal sulfide and metal oxide.
9. A method of making the cathode material of any one of claims 1~8 comprising the steps of:
(1) Mixing positive electrode active material, lithium-containing transition metal oxide and Ti 2 O 3 Carrying out ball milling reaction together;
(2) Carrying out heat treatment on the reaction product obtained in the step (1) at a certain temperature to obtain a positive electrode material;
the positive electrode material is of a core-shell structure, the core is a positive electrode active substance, and the shell comprises lithium-containing transition metal oxide and Ti 2 O 3 The lithium-containing transition metal oxide has an ionic conductivity of more than 10 -8 S·cm -1 The lithium-containing transition metal oxide can be delithiated to form an oxide at a voltage of more than 3.0V, and the electronic conductivity of the oxide is more than 10 -6 S·cm -1 。
10. The preparation method of claim 9, wherein the ball milling speed in the step (1) is 300rpm, and the ball milling time is 20h.
11. The method according to claim 9, wherein the heat treatment in the step (2) comprises a vacuum drying treatment and a high temperature treatment at 400-1000 ℃.
12. A solid-state lithium battery comprising the positive electrode material according to any one of claims 1 to 8 or the positive electrode material produced by the production method according to any one of claims 9 to 11.
13. The lithium solid state battery of claim 12, wherein the shell of the positive electrode material further comprises an oxide and TiO after the lithium solid state battery is charged 2 The oxide is obtained by delithiation conversion of the lithium-containing transition metal oxide.
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