CN111106344B - Composite positive electrode material, preparation method and lithium battery - Google Patents
Composite positive electrode material, preparation method and lithium battery Download PDFInfo
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Abstract
The invention provides a composite anode material which is Lix+y+ zMg(a‑x)/2Al(b‑y)/3M(c‑z)/4(P04)3The coated anode material is characterized in that M is one or more of Ti, Zr and Ge, x + y + z is more than or equal to 0 and less than 1, b-y is more than or equal to 0 and less than 1.5, a + b + c is 9, a magnesium-aluminum phosphate compound is used as a raw material and is coated on the surface of the anode material by a solid-phase, liquid-phase and gas-phase method, and the composite anode material which is the anode material, a doped layer and a coating layer is obtained after heat treatment. According to the invention, a small amount of lithium ions in the positive electrode material of the coating layer enter the coating layer, so that the ionic conductivity of the coating layer can be improved, meanwhile, metal in the coating layer can be partially doped on the surface of the positive electrode material to form a doped layer, so that the surface structure of the material is further stabilized, the double modification effects of surface coating and surface doping can be achieved, and the electrochemical performance of the positive electrode material, especially the high-capacity and high-voltage positive electrode material, can be effectively improved.
Description
Technical Field
The invention belongs to the field of lithium batteries, and particularly relates to a composite positive electrode material, a preparation method and a lithium battery.
Background
Due to rapid development of modern socioeconomic and science and technology, the performance of the traditional lithium ion battery can not meet the current energy requirement. The fields of rapidly developing electric automobiles, intelligent consumer electronics and the like all urgently need lithium ion batteries with higher energy density, long cycle life, low cost and high safety.
Currently, in the positive electrode field, high voltage and high capacity positive electrodes such as LiNi0.5Mn1.5O4、xLi2MnO3·(1-x)LiMO2(lithium-rich manganese-based), LiNi0.8Co0.1Mn0.1O2/LiNi0.8Co0.15Al0.05O2(NCM811/NCA) and high-voltage LiCoO2Is a positive electrode material with hopeful realization of high energy density. Go toThese material systems have been extensively studied, but currently, high energy density lithium ion batteries still have some problems, including cyclability, power, high and low temperature performance, and safety. Particularly for a high-voltage layered oxide positive electrode material, the surface activity of the material is higher under high voltage operation, and the material comprises an unstable surface structure, transition metal ions and oxygen ions in a high oxidation state, so that the surface structure of the material is rearranged, the transition metal is dissolved, the oxygen is separated out, and side reactions with an electrolyte are more severe, and the rapid failure of a battery is caused. Therefore, modification of the cathode material is required to improve its electrochemical performance and safety performance.
Coating materials metal phosphates such as GdPO4、Al(PO3)3The lithium ion battery is an ionic insulator, and the coating of the insulator on the surface of the positive electrode material can increase the lithium ion transmission of the positive electrode material to a certain extent, increase the polarization of the battery and influence the rate capability of the battery.
The pure surface coating layer only can play a role of physical barrier or HF absorbent, inhibit side reaction between the anode material and electrolyte and protect the surface of the material from being corroded. However, for high-capacity or high-voltage cathode materials, such as high-voltage lithium cobaltate and high-nickel ternary, large anisotropic changes of cell parameters occur during charging and discharging, which may cause irreversible phase change of the material, dislocation and other defects in the material, stress is generated, and finally the stress is released on the surface of the material, which causes phase change on the surface of the material, passivation layer formation, material cracking and the like. Therefore, the structural stability of the material is also important, and the crystal structure of the material needs to be stabilized by doping. If the surface coating is provided alone, it is not sufficient to suppress the structural destruction of the material, particularly, the structural destruction of the surface, and the long-term stability of the positive electrode material cannot be ensured.
The current reports of phosphate coated positive electrode materials, such as coated GdPO4，Al(PO3)3And the like, which have no ion conductivity, can reduce the ion conductivity of the surface of the material to a certain extent and increase the polarization of the material, and play a role in mainly isolating the mutual contact between the anode material and the electrolyte. The Li3PO4 coating, although it is an ionic conductor, is still only presentThe surface structure of the material cannot be sufficiently stabilized due to the function of the surface coating layer. For doping modification, such as co-doping modification of lanthanum and magnesium, and pure doping modification, the stability of the bulk phase structure of the material can be improved, but the side reaction of the surface of the material and an electrolyte cannot be sufficiently inhibited, and particularly, phase change, oxygen loss, transition metal dissolution, interface film growth and the like can rapidly occur on the surface of a high-voltage or high-activity cathode material, so that the performance of the material is degraded.
Disclosure of Invention
In view of this, the invention aims to provide a composite cathode material, a preparation method thereof and a lithium battery, which have better cycle stability, storage life, high-temperature performance, safety performance and rate capability.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a composite anode material is Lix+y+zMg(a-x)/2Al(b-y)/3M(c-z)/4(P04)3The coated anode material is characterized in that M is one or more of Ti, Zr and Ge, x + y + z is more than or equal to 0 and less than 1, b-y is more than or equal to 0 and less than 1.5, and a + b + c is 9.
A preparation method of a composite anode material comprises the steps of taking a magnesium-aluminum phosphate composite as a raw material, coating the magnesium-aluminum phosphate composite on the surface of an anode material by a solid-phase method, a liquid-phase method and a gas-phase method, carrying out heat treatment to obtain the composite anode material which sequentially comprises the anode material, a doping layer and a coating layer from inside to outside, uniformly coating the magnesium-aluminum phosphate composite on the surface of the anode material to form a continuous coating layer, and diffusing magnesium ions and/or aluminum ions and/or M in the coating layer of the magnesium-aluminum phosphate composite into the anode material to form the doping layer; the magnesium-aluminum phosphate compound accounts for 0.1% to less than or equal to 5% of the composite anode material in percentage by mass n.
Furthermore, the thickness of the cladding layer is 1-100nm, and the thickness of the doped layer is 1-100 nm.
Further, the positive electrode material is one or a mixture of more of lithium cobaltate with a layered structure, a ternary positive electrode material, a lithium-rich material, an olivine lithium iron phosphate material and a lithium nickel manganese oxide material with a spinel structure.
Further, when a solid-phase and liquid-phase method is adopted, the magnesium-aluminum phosphate compound serving as a raw material is Mga/2Alb/3Mc/4(PO4)3。
Further, when a gas phase method is adopted, the magnesium-aluminum phosphate compound serving as a raw material is Mga/2Alb/3Mc/4(PO4)3Or MgO, Al2O3、TiO2And NH4H2PO4A mixture of (a).
Further, the solid phase method comprises any one or combination of high-speed mixing, high-speed ball milling and mechanical fusion.
Further, the liquid phase method includes any one or a combination of evaporation, sol-gel, hydrothermal, spray drying, and precipitation.
Further, the vapor phase method comprises any one or a combination of atomic layer deposition, laser deposition, magnetron sputtering, chemical vapor deposition and physical vapor deposition.
Further, the heat treatment is carried out in a protective atmosphere of air, oxygen, nitrogen or argon at a temperature in the range of 100-800 ℃.
A lithium battery comprises a positive electrode, wherein the positive electrode comprises a composite positive electrode material, and the lithium battery comprises a liquid lithium ion battery, a mixed solid-liquid metal lithium battery, an all-solid lithium ion battery and an all-solid metal lithium battery.
High speed mixing, high speed ball milling, mechanical fusion, reaction temperature higher than 100 deg.c and lower than 1000 deg.c, and heat source selected from high speed shearing, high speed friction with grinding medium or external heating.
High speed mixing, high speed ball milling, mechanical fusion, and the reaction between positive electrode material and Mga/2Alb/3Mc/4(PO4)3At the contact point between them, by solid atomic or ionic diffusion, then gradually diffused into the reactant.
The solvent used in the evaporation method, the sol-gel method, the hydrothermal method, the spray drying method and the precipitation method comprises one or more of methanol, ethanol, propanol, ethylene glycol, benzyl alcohol, acetic acid, N-methyl pyrrolidone, acetone, acetonitrile, tetrahydrofuran, dimethyl carbonate, propylene carbonate, benzene, toluene, xylene, methyl ether, diethyl ether, ethylene glycol dimethyl ether and deionized water.
The evaporation method, the sol-gel method, the hydrothermal method and the spray drying method need external heating, the reaction temperature is higher than room temperature and lower than the boiling point of the solvent, and the solution is in a supersaturated state.
Sol-gel method, positive electrode material and Mga/2Alb/3Mc/4(PO4)3First dispersed in a solvent to form a low viscosity solution, uniformity at the molecular level can be achieved in a very short time.
The hydrothermal method needs to be carried out in a sealed pressure container, and the heating temperature is higher than 50 ℃ and lower than 300 ℃.
In the spray drying method, the solution can be atomized into fine fog drops, and the fine fog drops exchange heat with hot air flow with a certain flow rate to quickly evaporate the solvent.
Precipitation method using a precipitant to make the positive electrode material and Mg in liquid phasea/2Alb/3Mc/4(PO4)3Precipitating with one or more of ethylenediamine tetraacetic acid, dimethylglyoxime, 8-hydroxyquinoline, sodium tetraphenylborate, and quinoline.
Atomic layer deposition with MgO, Al2O3、MO2(M is one or more of Ti, Zr and Ge) and NH4H2PO4The target material is obtained by respectively depositing the anode material for different time under vacuum, voltage and argon environment, and finally calcining.
Laser deposition method with MgO, Al2O3、MO2(M is one or more of Ti, Zr and Ge) and NH4H2PO4The target material is prepared by respectively depositing different layers of anode materials in vacuum, oxygen environment and water cooling, and finally calcining.
Magnetron sputtering method with MgO, Al2O3、MO2(M is Ti, Zr, Ge)One or more) and NH4H2PO4The target material is prepared by sputtering the anode material in vacuum, under the condition of applying DC voltage and argon gas for different time, and calcining.
Chemical vapor deposition with MgO, Al2O3、MO2(M is one or more of Ti, Zr and Ge) and NH4H2PO4The target material is prepared by respectively depositing the anode material in vacuum, high temperature and argon environment for different time, and finally calcining.
Physical vapor deposition with Mga/2Alb/3Mc/4(PO4)3Is used as a target material and Mg is added in a vacuum environmenta/2Alb/3Mc/4(PO4)3Evaporated, then deposited on the surface of the cathode material, and finally calcined.
A small amount of lithium ions in the coating layer anode material enter into the coating layer, the ionic conductivity of the coating layer can be improved, meanwhile, metal in the coating layer can be partially doped on the surface of the anode material to form a doping layer, the surface structure of the material is further stabilized, the dual modification effects of surface coating and surface doping can be achieved, and the electrochemical performance of the anode material can be effectively improved for the anode material, particularly the anode material with high capacity and high voltage.
Compared with the prior art, the composite cathode material, the preparation method and the lithium battery have the following advantages:
1. the magnesium-aluminum phosphate composite has excellent chemical and electrochemical stability, and can effectively inhibit side reactions on the surface of the lithium anode;
2. a small amount of lithium ions in the positive electrode material permeate into the magnesium phosphate coating layer, so that the ion conduction characteristic of the coating layer is improved;
3. part of cations in the magnesium-aluminum phosphate coating layer are diffused into the anode material to form a doping layer, so that the crystal structure of the anode material is stabilized;
4. the composite anode material has better cycle stability, storage life, high-temperature performance, safety performance and rate capability.
Drawings
FIG. 1 is a schematic structural diagram of a composite positive electrode material;
fig. 2(a) is an SEM topography of LCO powder before coating;
FIG. 2(b) is an SEM topography of the coated LCO powder;
FIG. 3 is a graph of capacity development and capacity retention after cycling the LCO positive electrode material before and after modification (coating) for 100 weeks in a voltage range of 3-4.5V;
FIG. 4 is a graph of capacity development and capacity retention after cycling the LCO positive electrode material before and after modification (coating) for 100 weeks in a voltage range of 3-4.6V;
FIG. 5 is a graph showing the comparative capacity development in the case of charging and discharging at different rates of 3 to 4.5V.
1-a positive electrode material; 2-doping layer; and 3-coating layer.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to the following examples and accompanying drawings.
Example 1:
500g of Lithium Cobaltate (LCO) and 5g of Mg0.7Al0.4Ti1.6(P04)3Placing the two materials in a ball mill to fully mix, taking out the LCO material coated with the magnesium phosphate salt, placing the LCO material coated with the magnesium phosphate salt in a tubular furnace, heating the LCO material to 700 ℃ at the speed of 5 ℃/min in an argon environment, and preserving heat for 4 hours to obtain 1 wt% Lix+y+zMg(1.4-x)/2Al(1.2-y)/3Ti(6.4-z)/4(P04)3A coated LCO cathode material. The SEM topography of the LCO powder before coating is shown in fig. 2(a), and the SEM topography of the LCO powder after coating is shown in fig. 2 (b).
And respectively manufacturing the coated LCO and the LCO material before coating into a positive pole piece and manufacturing a button cell for performance comparison. Wherein the positive pole comprises the following components: composite positive electrode material: conductive additive: binder 92:3:5, using Celgard2300 type diaphragm, metal lithium cathode, EC/DMC +1M LiPF6Is an electrolyte. Under the circulation condition of 3-4.5V and 0.5C, the capacities of the two are kept as shown in figure 3, the capacity retention rate of the coated material after 100-week circulation is 95% under 3-4.5V, and the LCO capacity retention rate before modification is only 26%; under the circulation condition of 3-4.6V and 0.5C, the capacities of the two are kept as shown in FIG. 4, the capacity retention rate of the coated material after 100 cycles is 88.74% under 3-4.6V, and the capacity retention rate of the LCO before modification is only 30.27%, so that the modified LCO has better circulation performance under high voltage, because the structure and performance of the LCO are stabilized by the surface coating layer and the doping layer. In addition, since the coating layer has certain ionic conductivity, the magnification performance of the LCO modified at 4.5V is greatly improved, and the ratio of the magnification performance to the LCO before modification is shown in fig. 5.
Example 2:
500g of Lithium Cobaltate (LCO) and 5g of Mg0.7Al0.4Ti1.6(P04)3And adding 50% PVP solution, stirring at 700r/min for 2h, and drying. Placing the dried product in a tube furnace, heating to 700 ℃ at the speed of 5 ℃/min in an argon environment, and preserving heat for 4h to obtain 1 wt% Lix+y+zMg(1.4-x)/2Al(1.2-y)/3Ti(6.4-z)/4(P04)3A coated LCO cathode material.
Example 3:
1g of Lithium Cobaltate (LCO) was laid down on a substrate with Mg0.7Al0.4Ti1.6(P04)3Preparation materials of MgO and Al2O3、TiO2And NH4H2PO4As a target material, under a vacuum degree of 10-2Depositing for 28 seconds, 8 seconds, 64 seconds and 12 seconds respectively under the atmosphere of 24V, Ar torr and voltage, depositing different raw materials on the surface of a lithium cobaltate positive electrode, taking out deposited powder, heating to 700 ℃ at the speed of 5 ℃/min in an argon environment, and preserving heat for 4 hours to obtain the LiCoO2Over-coated Lix+y+zMg(1.4-x)/2Al(1.2-y)/ 3Ti(6.4-z)/4(P04)3The positive electrode material of (1).
Example 4:
500g of a ternary positive electrode (LiNi)0.8Co0.1Mn0.1O2) And 5g Mg0.7Al0.4Ti1.6(P04)3Placing the mixture in a ball mill to fully mix the two, taking out the ternary cathode material coated with the magnesium-aluminum phosphate, placing the ternary cathode material in a tubular furnace, heating the ternary cathode material to 700 ℃ at the speed of 5 ℃/min in an argon environment, and preserving the temperature for 4 hours to obtain the 1 wt% Lix+y+zMg(1.4-x)/2Al(1.2-y)/ 3Ti(6.4-z)/4(P04)3A coated ternary positive electrode material.
Example 5:
500g of a ternary positive electrode (LiNi)0.8Co0.1Mn0.1O2) And 5g Mg0.7Al0.4Ti1.6(P04)3And adding 50% PVP solution, stirring at 700r/min for 2h, and drying. Placing the dried product in a tube furnace, heating to 700 ℃ at the speed of 5 ℃/min in an argon environment, and preserving heat for 4h to obtain 1 wt% Lix+y+zMg(1.4-x)/2Al(1.2-y)/3Ti(6.4-z)/4(P04)3A coated ternary positive electrode material.
Example 6:
1g of a ternary positive electrode (LiNi)0.8Co0.1Mn0.1O2) Spread on a substrate with Mg0.7Al0.4Ti1.6(P04)3Preparation material MgO and Al2O3、TiO2And NH4H2PO4As a target material, under a vacuum degree of 10-2Depositing for 28 seconds, 8 seconds, 64 seconds and 12 seconds respectively under the atmosphere of 24V, Ar torr and voltage, depositing different raw materials on the surface of the ternary positive electrode, taking out deposited powder, heating to 700 ℃ at the speed of 5 ℃/min in an argon environment, and preserving heat for 4 hours to obtain the 0.5 percent Li coated on the ternary positive electrodex+y+zMg(1.4-x)/2Al(1.2-y)/3Ti(6.4-z)/4(P04)3Positive electrode material of (2)。
Example 7:
500g of a lithium-rich manganese-based positive electrode material (Li)1.2Ni0.13Co0.13Mn0.54O2) And 5g Mg0.7Al0.4Ti1.6(P04)3Placing the mixture in a ball mill to fully mix the mixture, taking out the lithium manganate material coated with the magnesium aluminum phosphate, placing the mixture in a tubular furnace, heating the mixture to 700 ℃ at the speed of 5 ℃/min in an argon environment, and preserving the heat for 4 hours to obtain the 1 wt% Lix+y+zMg(1.4-x)/ 2Al(1.2-y)/3Ti(6.4-z)/4(P04)3And (3) a coated lithium-rich manganese-based positive electrode material.
Example 8:
500g of a lithium-rich manganese-based positive electrode material (Li)1.2Ni0.13Co0.13Mn0.54O2) And 5g Mg0.7Al0.4Ti1.6(P04)3And adding 50% PVP solution, stirring at 700r/min for 2h, and drying. Placing the dried product in a tube furnace, heating to 700 ℃ at the speed of 5 ℃/min in an argon environment, and preserving heat for 4h to obtain 1 wt% Lix+y+zMg(1.4-x)/2Al(1.2-y)/ 3Ti(6.4-z)/4(P04)3And (3) a coated lithium-rich manganese-based positive electrode material.
Example 9:
1g of a lithium-rich manganese-based positive electrode material (Li)1.2Ni0.13Co0.13Mn0.54O2) Spread on a substrate with Mg0.7Al0.4Ti1.6(P04)3Preparation material MgO, Al2O3、TiO2And NH4H2PO4As a target material, under a vacuum degree of 10-2Depositing for 28 seconds, 8 seconds, 64 seconds and 12 seconds respectively under the atmosphere of 24V, Ar torr and voltage, depositing different raw materials on the surface of a traditional anode, taking out deposited powder, heating to 700 ℃ at the speed of 5 ℃/min in an argon environment, and preserving heat for 4 hours to obtain the 0.5 percent Li coated on the lithium-rich manganese-based anodex+y+zMg(1.4-x)/2Al(1.2-y)/3Ti(6.4-z)/4(P04)3The positive electrode material of (1).
Comparative example 1:
500g of Lithium Cobaltate (LCO) and 5g of Al2O3Placing the mixture in a ball mill to fully mix the two, taking out the lithium manganate material coated with the magnesium phosphate salt, placing the lithium manganate material in a tubular furnace, heating the mixture to 700 ℃ at the speed of 5 ℃/min in an argon environment, and preserving the temperature for 4 hours to obtain 1 wt% Al2O3The coated composite LCO cathode material with the core-shell structure.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (5)
1. A composite positive electrode material characterized in that: the composite anode material is Lix+y+zMg(a-x)/2Al(b-y)/3M(c-z)/4(P04)3The coated anode material, M is one or more of Ti, Zr and Ge, x + y + z is more than or equal to 0 and less than 1, b-y is more than or equal to 0 and less than 1.5, a + b + c is 9,
the preparation method of the composite cathode material comprises the following steps: the method comprises the following steps of coating a magnesium-aluminum phosphate compound serving as a raw material on the surface of a positive electrode material by a solid-phase method, a liquid-phase method and a gas-phase method, performing heat treatment to obtain a composite positive electrode material which sequentially comprises the positive electrode material, a doping layer and a coating layer from inside to outside, uniformly coating the magnesium-aluminum phosphate compound on the surface of the positive electrode material to form a continuous coating layer, and diffusing magnesium ions and/or aluminum ions and/or M in the coating layer of the magnesium-aluminum phosphate compound into the positive electrode material to form the doping layer; the mass percentage n of the magnesium-aluminum phosphate compound in the composite anode material is 0.1 percent and less than or equal to 5 percent,
when a solid-phase and liquid-phase method is adopted, the magnesium-aluminum phosphate compound serving as the raw material is Mga/2Alb/3Mc/4(PO4)3(ii) a When a gas phase method is adopted, the magnesium-aluminum phosphate compound serving as a raw material is Mga/2Alb/3Mc/4(PO4)3Or MgO, Al2O3、TiO2And NH4H2PO4The mixture of (a) and (b),
the solid phase method comprises any one or combination of high-speed mixing, high-speed ball milling and mechanical fusion,
the liquid phase method comprises any one or combination of an evaporation method, a sol-gel method, a hydrothermal method, a spray drying method and a precipitation method,
the gas phase method comprises any one or combination of an atomic layer deposition method, a laser deposition method, a magnetron sputtering method, a chemical vapor deposition method and a physical vapor deposition method.
2. The composite positive electrode material according to claim 1, characterized in that: the thickness of the coating layer is 1-100nm, and the thickness of the doped layer is 1-100 nm.
3. The composite positive electrode material according to claim 1, characterized in that: the positive electrode material is one or a mixture of more of lithium cobaltate with a layered structure, a ternary positive electrode material, a lithium-rich material, an olivine lithium iron phosphate material and a lithium nickel manganese oxide material with a spinel structure.
4. The composite positive electrode material according to claim 1, characterized in that: the heat treatment is carried out in a protective atmosphere of air, oxygen, nitrogen or argon at a temperature in the range of 100-800 ℃.
5. A lithium battery, characterized in that: the composite cathode material comprises a cathode, the cathode comprises the composite cathode material of claim 1, and the lithium battery comprises a liquid lithium ion battery, a mixed solid-liquid metal lithium battery, an all-solid lithium ion battery and an all-solid metal lithium battery.
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