CN110635132A - Divalent metal phosphate powder and lithium metal phosphate powder for lithium ion battery and method for preparing the same - Google Patents
Divalent metal phosphate powder and lithium metal phosphate powder for lithium ion battery and method for preparing the same Download PDFInfo
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- CN110635132A CN110635132A CN201910386552.3A CN201910386552A CN110635132A CN 110635132 A CN110635132 A CN 110635132A CN 201910386552 A CN201910386552 A CN 201910386552A CN 110635132 A CN110635132 A CN 110635132A
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- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/265—General methods for obtaining phosphates
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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Abstract
A divalent metal phosphate powder and a lithium metal phosphate powder for a lithium ion battery and a method for preparing the same. The divalent metal phosphate powder is represented by the following formula (I): (Fe)l‑xMx)3(PO4)2·yH2O (I), wherein M comprises at least one metal selected from the group consisting of Mn, Co, Ni, Cu, Cr, V, Mo, Ti, Zn, Zr, Tc, Ru, Rh, Pd, Ag, Cd, Pt, Au, Cu, Mo, Ti, Zn, Ti, Cu, Ti, Zn,Al, Ga, In, Be, Mg, Ca, Sr, B and Nb, x is more than 0.5 and less than or equal to 1, y is an integer from 0 to 8, the divalent metal phosphate powder is composed of a plurality of flakes, and the length of each flake is between 50nm and 10 μm.
Description
Technical Field
The invention relates to divalent metal phosphate powder and lithium metal phosphate powder for a lithium ion battery and a preparation method thereof. In particular, the present invention relates to a divalent metal phosphate powder for preparing a lithium ion battery having a large length/thickness ratio and a lithium metal phosphate powder prepared therefrom, and a preparation method thereof.
Background
With the development of various portable electronic devices, energy storage technology has gained more and more attention due to the fact that batteries are the main power source of portable electronic devices. Among commercially available batteries, the secondary battery having a small volume is particularly useful as a main power supply device for portable electronic devices such as mobile phones and notebook computers. In addition, the secondary battery can be used not only for portable electronic devices, but also for electric power transportation vehicles.
In the development of secondary batteries, lithium secondary batteries (also referred to as lithium ion batteries) completed in 1990 are the most widely used batteries nowadays. First lithium secondary batteries used LiCoO2As a cathode material. LiCoO2Including a high operating voltage and a stable charge/discharge voltage, and thus LiCoO is used2Secondary batteries as cathode materials are widely used in portable electronic devices. Then, LiFePO having an olivine structure was developed4And LiMn having a spinel structure2O4A cathode material for a lithium secondary battery. Compared with LiCoO2Using LiFePO4Or LiMn2O4As a cathode material for a secondary battery, it is possible to improve the safety of the battery, increase the number of charge/discharge cycles, and be less expensive.
Although LiMn is used2O4The battery as a cathode material has lower cost and can improve safety, but LiMn is used due to the ginger-taylor (Jahn-Teller) effect2O4The spinel structure of (a) may disintegrate during deep discharge. If so, the cycle performance of the battery may be further reduced. If LiFePO is used4As a cathode material for a battery, the battery also has characteristics of lower cost and improved safety. Further, LiFePO4Has a capacitance higher than LiMn2O4Thus using LiFePO4The prepared battery can be further used for batteries requiring larger current and higher powerProvided is a device. Further, LiFePO4Non-toxic and environmentally friendly materials, and has better high temperature characteristics. Thus, LiFePO4Is an excellent cathode material of lithium battery. LiFePO is currently used4The average discharge voltage of the lithium battery used as the cathode material is 3.2-3.4 volts (V) vs. Li+/Li。
The conventional lithium ion battery structure includes: a cathode, an anode, a separator, and an electrolyte containing lithium. The lithium ion battery performs charge/discharge of the battery according to an embedding-extracting mechanism of lithium, and the charge/discharge mechanism is shown in the following equations (I) and (II):
charging: LiFePO4-x Li+-xe-→xFePO4+(1-x)LiFePO4 (I)
Discharging: FePO4+x Li++xe-→x LiFePO4+(1-x)FePO4 (II)
LiFePO for lithium ion deintercalation during charging4The structure of (1), and is embedded in FePO during discharging4The structure of (1). Charging/discharging a LiFePO of a lithium ion battery4/FePO4Two-phase process of (a).
LiFePO4Powders are currently often prepared in a solid state process, but the product properties are highly correlated with the thermal annealing temperature of the solid state process. If the thermal annealing temperature is lower than 700 ℃, all the raw materials need to be uniformly mixed; if the raw materials are not uniformly mixed, LiFePO4Fe will be present in the powder3+Impurities. If the thermal annealing temperature is lower than 600 ℃, LiFePO4The average particle size will be less than 30 microns (μm); however, if the thermal annealing temperature is increased, LiFePO4The average particle size will be greater than 30 μm. If LiFePO4If the average particle size is larger than 30 μm, additional grinding and screening steps are required to obtain a powder with a specific particle size of 1 μm to 10 μm for the preparation of lithium ion batteries. Thus, if LiFePO is prepared in the solid state process4The powder requires additional grinding and screening steps, which may increase the cost of the lithium ion battery and may also produce LiFePO4Excessive and uneven particle size of the powder.
Furthermore, LiFePO4、LiMnPO4、LiNiPO4And LiCoPO4With an olivine structure and similar theoretical capacitance, but with different theoretical voltage platforms (voltage platforms). For example, LiFePO4The voltage platform is 3.4V, LiMnPO4Voltage plateau of 4.1V, LiCoPO4A voltage plateau of 4.8V, and LiNiPO4The voltage plateau was 5.6V. Compared with LiFePO4Although LiMnPO was present4、LiNiPO4And LiCoPO4Has higher theoretical mass-energy density (mass-energy density), but LiMnPO4、LiNiPO4And LiCoPO4Is less conductive and transfers LiMnPO4、LiNiPO4And LiCoPO4Has poor lithium ion capacity, resulting in the use of LiMnPO4、LiNiPO4And LiCoPO4The battery of (a) has a substantially lower capacitance.
Therefore, there is a need to provide a simple method for preparing a micron-sized, sub-micron-sized, or even nano-sized cathode material for lithium ion batteries to increase the charge/discharge efficiency and mass-energy density of the battery and reduce the cost thereof.
Disclosure of Invention
The object of the present invention is to provide a divalent metal phosphate powder for the preparation of electrode materials, in particular cathode materials, for lithium ion batteries, wherein the divalent metal phosphate powder has a nano-, micro-, or sub-micro particle size and a large length/thickness ratio and is usable in the present day process for the preparation of lithium metal phosphate powders, and a method for the preparation thereof.
Another object of the present invention is to provide a lithium metal phosphate powder for a lithium ion battery and a method for preparing the same, in which the divalent metal phosphate powder of the present invention is used to prepare the lithium metal phosphate powder. Thus, the thermally annealed powder has a uniform and small nano-, micro-, or sub-micron particle size, which may save grinding and screening steps. Furthermore, the obtained lithium metal phosphate powder has a larger length/thickness ratio, and can improve the charge/discharge efficiency of the lithium ion battery.
To achieve the above object, the method for preparing a divalent metal phosphate powder according to the present invention comprises the steps of: (A) providing a phosphorus-containing precursor solution, wherein the phosphorus-containing precursor solution comprises: a phosphorus-containing precursor and a weak base compound; and (B) adding at least one divalent metal compound into the phosphorus-containing precursor solution to obtain divalent metal phosphate powder.
In addition, the invention also provides divalent metal phosphate powder prepared by the method, which can be used for preparing electrode materials of lithium ion batteries. The divalent metal phosphate powder for preparing an electrode material for a lithium ion battery of the present invention is represented by the following formula (I):
(Fel-xMx)3(PO4)2·yH2O (I)
wherein M comprises at least one metal selected from the group consisting of Mn, Co, Ni, Cu, Cr, V, Mo, Ti, Zn, Zr, Tc, Ru, Rh, Pd, Ag, Cd, Pt, Au, Al, Ga, In, Be, Mg, Ca, Sr, B, and Nb; x is more than 0.5 and less than or equal to 1; an integer of y0 to 8; the divalent metal phosphate powder is composed of a plurality of flaky powders; and the length of each flake is between 50nm and 10 μm.
In addition, the present invention also provides a method for preparing lithium metal phosphate powder for a lithium ion battery, wherein the divalent metal phosphate powder is used as an iron-containing precursor. The method for preparing lithium metal phosphate powder according to the present invention comprises the steps of: (a) providing the divalent metal phosphate powder; (b) mixing the divalent metal phosphate powder and a lithium-containing precursor to obtain a mixed powder; and (c) heat-treating the mixed powder to obtain a lithium metal phosphate powder.
When the aforementioned method for preparing the lithium metal phosphate powder of the present invention is used, the lithium metal phosphate powder of the present invention is obtained as shown in the following formula (II):
LiFe1-aMaPO4 (II)
wherein M comprises at least one metal selected from the group consisting of Mn, Co, Ni, Cu, Cr, V, Mo, Ti, Zn, Zr, Tc, Ru, Rh, Pd, Ag, Cd, Pt, Au, Al, Ga, In, Be, Mg, Ca, Sr, B, and Nb; a is more than 0.5 and less than or equal to 1; the lithium metal phosphate powder is composed of a plurality of flakes; and the length of each flake is between 50nm and 10 μm.
The divalent metal phosphate powder used for preparing the electrode material of the lithium ion battery has uniform and small nano, micron or submicron particle size, and particularly has a larger length/thickness ratio. However, the conventional divalent metal phosphate powder or the conventional ferrous phosphate precursor has large and uneven sizes, and thus, the thermal annealing step (i.e., the thermal treatment step) must last for at least 10 hours to completely convert the divalent metal phosphate powder or the ferrous phosphate precursor into lithium metal phosphate or lithium iron phosphate. Furthermore, the particle size of conventional thermally annealed powders is generally large, so that a grinding and screening step must be carried out to obtain a powder with a size between 1 μm and 10 μm. However, the divalent metal phosphate powder of the present invention has a uniform and small size and a large length/thickness ratio, as well as a specific shape. Therefore, the divalent metal phosphate powder can be completely converted into lithium metal phosphate within several hours (less than 10 hours), and the time required for the thermal annealing step can be greatly reduced. In addition, after the thermal annealing step, the obtained lithium metal phosphate powder still has a similar size and a similar shape to the divalent metal phosphate powder, so that the electrode material of the lithium ion battery can be obtained without grinding and screening. Therefore, if the divalent metal phosphate powder of the present invention is used to prepare a lithium metal phosphate powder, the thermal annealing time can be reduced, and the milling and screening steps can also be omitted. Therefore, the cost for manufacturing the lithium ion battery can be further reduced. In addition, the divalent metal phosphate powder of the present invention can be directly used in the current lithium metal phosphate powder production line, so that the lithium metal phosphate powder can be prepared by using the divalent metal phosphate powder of the present invention without establishing a new production line. Thus, the cost of manufacturing the lithium ion battery can be further reduced.
The divalent metal phosphate powder or lithium metal phosphate powder of the present invention is a separate flake, a flake in which one ends of the flakes are connected to each other, a flake in which centers are connected to each other, or a flake in which one ends of the flakes are connected to each other to form a connection center. In one embodiment of the invention, the flakes are individual flakes. In another embodiment of the invention, the flakes are connected to each other to form a connection center.
In addition, in the divalent metal phosphate powder or lithium metal phosphate powder of the present invention, the length of each flake may be between 50nm and 10 μm. For example, the length of each flake powder may be 50nm to 10 μm, 50nm to 5 μm, 50nm to 3 μm, 50nm to 2 μm, 50nm to 1 μm, 50nm to 900nm, 50nm to 800nm, 50nm to 700nm, 50nm to 600nm, 50nm to 500nm, 50nm to 400nm, 50nm to 300nm, 100nm to 10 μm, 100nm to 5 μm, 100nm to 3 μm, 100nm to 2 μm, 100nm to 1 μm, 100nm to 900nm, 100nm to 800nm, 100nm to 700nm, 100nm to 600nm, 100nm to 500nm, 100nm to 400nm, 100nm to 300nm, 200nm to 10 μm, 200nm to 5 μm, 200nm to 3 μm, 200nm to 2 μm, 200nm to 1 μm, 200nm to 900nm, 200nm to 800nm, 200nm to 200nm, 200 to 5 μm, 200nm to 300nm, 200 to 1 μm, 200nm, 200 to 300nm, or 300nm, 300nm to 3 mu m, 300nm to 2 mu m, 300nm to 1 mu m, 300nm to 900nm, 300nm to 800nm, 300nm to 700nm, 300nm to 600nm, 300nm to 500nm, 300nm to 400nm, 400nm to 10 mu m, 400nm to 5 mu m, 400nm to 3 mu m, 400nm to 2 mu m, 400nm to 1 mu m, 400nm to 900nm, 400nm to 800nm, 400nm to 700nm, 400nm to 600nm or 400nm to 500 nm.
In addition, in the divalent metal phosphate powder or lithium metal phosphate powder of the present invention, the thickness of each flake may be between 5nm and 1 μm. For example, the thickness of each flake powder may be 5nm to 1 μm, 5nm to 900nm, 5nm to 800nm, 5nm to 700nm, 5mm to 600nm, 5nm to 500nm, 5nm to 400nm, 5nm to 300nm, 5nm to 200nm, 5nm to 150nm, 5nm to 140nm, 5nm to 130nm, 5nm to 120nm, 5nm to 110nm, 5nm to 100nm, 5nm to 90nm, 5nm to 80nm, 5nm to 70nm, 5nm to 60nm, 5nm to 50nm, 5nm to 40nm, 5nm to 30nm, 5nm to 25nm, 5nm to 20nm, 5nm to 15nm, 5nm to 10nm, 10nm to 1 μm, 10nm to 900nm, 10nm to 800nm, 10nm to 700nm, 10nm to 600nm, 10nm to 500nm, 10 to 400nm, 10 to 300nm, 10 to 200 μm, 10nm to 900nm, 10nm to 140nm, 10 to 100nm, 10 to 100nm, or more, 10nm to 90nm, 10nm to 80nm, 10nm to 70nm, 10nm to 60nm, 10nm to 50nm, 10nm to 40nm, 10nm to 30nm, 10nm to 25nm, 10nm to 20nm, 10nm to 15nm, 15nm to 1 μm, 15nm to 900nm, 15nm to 800nm, 15nm to 700nm, 15nm to 600nm, 15nm to 500nm, 15nm to 400nm, 15nm to 300nm, 15nm to 200nm, 15nm to 150nm, 15nm to 140nm, 15nm to 130nm, 15nm to 120nm, 15nm to 110nm, 15nm to 100nm, 15nm to 90nm, 15nm to 80nm, 15nm to 70nm, 15nm to 60nm, 15nm to 50nm, 15nm to 40nm, 15nm to 30nm, 15nm to 25nm, 15nm to 20nm, 20nm to 1 μm, 20nm to 80nm, 20nm to 20nm, 20nm to 300nm, 15nm to 200nm, 15nm to 300nm, 15nm to 20nm, 15 to 140nm, 15nm to 20nm, 15nm to 120nm, 20 nm-150 nm, 20 nm-140 nm, 20 nm-130 nm, 20 nm-120 nm, 20 nm-110 nm, 20 nm-100 nm, 20 nm-90 nm, 20 nm-80 nm, 20 nm-70 nm, 20 nm-60 nm, 20 nm-50 nm, 20 nm-40 nm, 20 nm-30 nm, 30 nm-1 μm, 30 nm-900 nm, 30 nm-800 nm, 30 nm-700 nm, 30 nm-600 nm, 30 nm-500 nm, 30 nm-400 nm, 30 nm-300 nm, 30 nm-200 nm, 30 nm-150 nm, 30 nm-140 nm, 30 nm-130 nm, 30 nm-120 nm, 30 nm-110 nm, 30 nm-100 nm, 30 nm-90 nm, 30 nm-80 nm, 30 nm-70 nm, 30 nm-60 nm, 30 nm-50 nm, 30 nm-40 nm, 40 nm-1 μm, 40-100 nm, 40-40 nm, 40-200 nm, 300nm, 30 nm-200 nm, 30 nm-150 nm, 30 nm-100 nm, 30 nm-200 nm, 30 nm-100 nm, 30 nm-50 nm, 30 nm-40 nm, 40-200 nm, 300nm, 100, 40nm to 150nm, 40nm to 140nm, 40nm to 130nm, 40nm to 120nm, 40nm to 110nm, 40nm to 100nm, 40nm to 90nm, 40nm to 80nm, 40nm to 70nm, 40nm to 60nm or 40nm to 50 nm.
In the divalent metal phosphate powder or lithium metal phosphate powder of the present invention, the length/thickness ratio of each flake may be between 10 and 500. For example, the ratio of length/thickness of each flake powder may be 10 to 500, 10 to 400, 10 to 300, 10 to 200, 10 to 150, 10 to 130, 10 to 100, 10 to 90, 10 to 80, 10 to 70, 10 to 60, 10 to 50, 10 to 40, 1O to 30, 10 to 20, 10 to 15, 20 to 500, 20 to 400, 20 to 300, 20 to 200, 20 to 150, 20 to 130, 20 to 100, 20 to 90, 20 to 80, 20 to 70, 20 to 60, 20 to 50, 20 to 40, 20 to 30, 30 to 500, 30 to 400, 30 to 300, 30 to 200, 30 to 150, 30 to 130, 30 to 100, 30 to 90, 30 to 80, 30 to 70, 30 to 60, 30 to 50, 30 to 40, 40 to 500, 40 to 400, 40 to 300, 40 to 200, 40 to 150, 40 to 130, 40 to 100, 40 to 90, 40 to 40, 40 to 70, 40 to 50, 50 to 50, 30 to 50, 50 to 50, 30 to 500, 40 to 300, 40 to, 50 to 150, 50 to 130, 50 to 100, 50 to 90, 50 to 80, 50 to 70 or 50 to 60.
When the thickness of the divalent metal phosphate powder is in the nanometer level, the thermal annealing time for preparing the lithium metal phosphate powder can be greatly reduced, and the steps of grinding and screening can be omitted. In addition, if the thickness of the lithium metal phosphate powder is also in the order of nanometers, the charge/discharge efficiency of the obtained lithium ion battery can be further improved.
Further, the divalent metal phosphate powder of the present invention may crystallize the divalent metal phosphate powder with a crystallinity of more than 10%.
In the method for preparing the divalent metal phosphate powder of the present invention, the divalent metal compound may Be any metal salt containing Fe, Mn, Co, Ni, Cu, Cr, V, Mo, Ti, Zn, Zr, Tc, Ru, Rh, Pd, Ag, Cd, Pt, Au, Al, Ga, In, Be, Mg, Ca, Sr, B and/or Nb. Preferably, the divalent metal compound may Be a sulfate, carbonate, nitrate, oxalate, acetate, chlorite, bromide, or iodide of Fe, Mn, Co, Ni, Cu, Cr, V, Mo, Ti, Zn, Zr, Tc, Ru, Rh, Pd, Ag, Cd, Pt, Au, Al, Ga, In, Be, Mg, Ca, Sr, B, or Nb. More preferably, the divalent metal compound may be a sulfate, carbonate, nitrate, oxalate, acetate, chlorite, bromide, or iodide of Fe, Mn, Co, Cu, Ni, Zn, or Mg. Therefore, in one embodiment of the present invention, M of formula (I) may include at least one metal selected from the group consisting of Mn, Co, Cu, Ni, Zn and Mg. In another embodiment of the present invention, M of the formula (II) may include at least one metal selected from the group consisting of Mn, Co, Cu, Ni, Zn and Mg.
In one embodiment of the present invention, M in the formula (I) can be Mn, Co, Ni or Cu, and x is 0.6 ≦ x ≦ 1. In another embodiment of the present invention, the divalent metal phosphate powder is represented by the following formula (I-1):
(Fe1-x1-x2Mnx1M’x2)3(PO4)2·yH2O (I-1)
wherein M' comprises at least one metal selected from the group consisting of Co, Cu, Ni, Zn and Mg; x1 is more than or equal to 0.2 and less than or equal to 0.8; x2 is more than or equal to 0.05 and less than or equal to 0.4; x1+ x2 is more than 0.5 and less than or equal to 1; and integers of y0 to 8.
In one embodiment of the present invention, M in the formula (II) can be Mn, Co, Ni or Cu, and a is 0.6 ≦ a ≦ 1. In another embodiment of the invention, M of the formula (II) is Mn, and 0.5 < a < 1. For example, 0.5 < a < 0.99, 0.6. ltoreq. a < 1, or 0.6. ltoreq. a < 0.99. In another embodiment of the present invention, the lithium metal phosphate powder is represented by the following formula (II-1):
LiFe1-al-a2Mna1M’a2PO4 (II-1)
wherein M' comprises at least one metal selected from the group consisting of Co, Cu, Ni, Zn, and Mg; a1 is more than or equal to 0.2 and less than or equal to 0.8; a2 is more than or equal to 0.05 and less than or equal to 0.4; and 0.5 & lt a1+ a2 & lt 1.
The method for preparing a divalent metal phosphate powder according to the present invention may further comprise the step (c) after the step (b): washing the divalent metal phosphate powder. Wherein the divalent metal phosphate powder may be washed using ethanol, water, or a combination thereof. Preferably, the divalent metal phosphate powder is washed with deionized water. In addition, the method for preparing a divalent metal phosphate powder according to the present invention may further include step (d) after step (c): the obtained divalent metal phosphate powder is dried. As the temperature of the drying step increases, its time taken may be reduced. Preferably, the divalent metal phosphate powder is dried at 40-120 ℃ for 10-120 hours. More preferably, the divalent metal phosphate powder is dried at 50-70 ℃ for 10-120 hours.
The lithium metal phosphate powder of the present invention has an olivine structure. In one embodiment of the present invention, the obtained lithium metal phosphate powder has an X-ray diffraction pattern consistent with that of a lithium metal phosphate standard. In another embodiment of the present invention, at least one diffraction peak of the X-ray diffraction pattern of the obtained lithium metal phosphate powder may be slightly shifted compared to the lithium metal phosphate standard.
In one embodiment of the present invention, the obtained divalent metal phosphate powder has an X-ray diffraction pattern consistent with that of the divalent metal phosphate standard. In another embodiment of the present invention, at least one diffraction peak of the X-ray diffraction pattern of the obtained divalent metal phosphate powder may be slightly shifted compared to the divalent metal phosphate standard.
In addition, in the method for preparing the divalent metal phosphate powder, the phosphorus-containing precursor may be selected from H3PO4、NaH2PO4、Na2HPO4、Mg3(PO4)2And NH4H2PO4At least one of the group consisting of. Preferably, the phosphorus-containing precursor may be H3PO4、NH4H2PO4Or a combination thereof.
Further, in the method for preparing a divalent metal phosphate powder of the present invention, the weak base compound may be Na2CO3、NaHCO3Or a combination thereof. Preferably, the weak base compound can be NaHCO3。
In the method for preparing the lithium metal phosphate powder of the present invention, the lithium-containing precursor may be selected from the group consisting of LiOH, Li2CO3、LiNO3、CH3COOLi、Li2C2O4、Li2SO4、LiCl、LiBr、LiI、LiH2PO4、Li2HPO4And Li3PO4At least one of the group consisting of. Preferably, the lithium-containing precursor LiOH, Li2SO4、LiH2PO4Or Li3PO4. More preferably, the lithium-containing precursor is Li3PO4。
In addition, in the method for preparing a lithium metal phosphate powder of the present invention, the divalent metal phosphate powder is mixed with the lithium-containing precursor and at least one carbonaceous material to obtain the mixed powder in step (b). Here, the surface of the obtained lithium metal phosphate powder is coated with carbon, so that the conductivity of the obtained lithium metal phosphate powder can be increased. In addition, the carbonaceous material can also inhibit the growth of the lithium metal phosphate powder, so that the small size of the lithium metal phosphate powder can be maintained. Here, the carbonaceous material may be any carbohydrate (e.g., sucrose), stearic acid, citric acid, lauric acid, polystyrene spheres (PS spheres), graphene oxide, or vitamin C (L-ascorbic acid). In addition, the amount of the carbonaceous material additionally added may be 0.1 to 40 wt% of the weight of the obtained lithium metal phosphate powder. Preferably, the amount of the carbon-containing material additionally added may be 2.5 to 30 wt% of the weight of the obtained lithium metal phosphate powder.
In the method for preparing lithium metal phosphate powder of the present invention, one or more types of the divalent metal phosphate powder may be used in step (b). In one embodiment of the present invention, if the lithium metal phosphate powder is to comprise a metal, one type of the divalent metal phosphate powder may be used in step (b). In another embodiment of the present invention, if the lithium metal phosphate powder is required to contain a metalloid, a class of the divalent metal phosphate powder containing a metalloid can be used in step (b); alternatively, one type of the divalent metal phosphate powder comprising one metal and another type of the divalent metal phosphate powder comprising another metal may be used in step (b). However, the present invention is not limited thereto, and the use of the divalent metal phosphate powder may be adjusted depending on the metal that the lithium metal phosphate powder is required to contain.
In the method for preparing lithium metal phosphate powder of the present invention, the mixed powder may be heat-treated in an atmosphere or vacuum, or introduced with a gas stream to obtain lithium metal phosphate powder in step (c). In another embodiment, the mixed powder may be heat-treated by introducing a gas flow to obtain a lithium metal phosphate powder, and the gas pressure of the introduced gas flow is about 1 atm. In another embodiment, a vacuum state may be formed in a heating tube, and then a gas may be introduced into the heating tube to close the heating tube for heat treatment, so as to obtain the lithium metal phosphate powder, wherein the pressure in the heating tube should be maintained below 1atm during the heat treatment. In still another embodiment, the heating tube may be closed without introducing gas while making a vacuum state in the heating tube, and then heat-treated to obtain lithium metal phosphate powder. Here, the atmosphere or introduced gas may be usedFor the protective gas or reducing gas, it may comprise a gas selected from the group consisting of N2、H2He, Ne, Ar, Kr, Xe, CO, methane, Ar-H2And N2-H2At least one of the group consisting of mixed gases, or a combination thereof. Preferably, the protective gas or reducing gas N2、H2、Ar、Ar-H2Or N2-H2And (4) mixing the gases. More preferably, the protective gas or reducing gas is N2-H2Or Ar-H2And (4) mixing the gases.
Further, in the method for preparing the lithium metal phosphate powder of the present invention, the mixed powder is preferably heat-treated at 900 ℃ at 300-. Further, the mixed powder is preferably heat-treated for 1 to 20 hours. More preferably, the mixed powder is heat treated at 500-860 ℃ for 2-10 hours.
The lithium metal phosphate powder obtained in the present invention can be used in electrode materials (e.g., cathode materials) to prepare lithium ion batteries, in conjunction with any of the methods of the prior art. A method of preparing a lithium ion battery is briefly described herein, but the present invention is not limited thereto.
An anode and a cathode are provided. Here, the anode is an anode made of a lithium metal plate or a carbon material by coating a carbon material on an anode current collector and drying and pressing the carbon material to form an anode of a lithium ion battery. The cathode current collector is coated with a cathode active material (e.g., the lithium metal phosphate powder of the present invention), which is dried and extruded to form the cathode of the lithium ion battery. Then, a separator is inserted between the anode and the cathode, and a lithium-containing electrolyte is injected, so that the lithium ion battery can be obtained after assembly.
Other objects, advantages and novel features of the invention will become apparent from the following detailed description of the invention when considered in conjunction with the drawings.
Drawings
FIG. 1 shows Mn prepared in example 14 of the present invention3(PO4)2SEM picture of (1);
FIG. 2 shows Co prepared in example 16 of the present invention3(PO4)2SEM picture of (1);
FIG. 3 is Cu prepared according to example 17 of the present invention3(PO4)2SEM picture of (1);
FIG. 4 shows (Mn) produced in example 3 of the present invention0.8Fe0.1Mg0.1)3(PO4)2SEM picture of (1);
FIG. 5 shows (Mn) produced in example 1 of the present invention0.8Fe0.1Co0.1)3(PO4)2SEM picture of (1);
FIG. 6 shows (Mn) produced in example 2 of the present invention0.8Fe0.1Zn0.1)3(PO4)2SEM picture of (1);
FIG. 7 shows (Mn) produced in example 4 of the present invention0.8Fe0.1Ni0.1)3(PO4)2SEM picture of (1);
FIG. 8 shows (Mn) produced in example 5 of the present invention0.6Fe0.2Ni0.2)3(PO4)2SEM picture of (1);
FIG. 9 is (Mn) prepared in example 6 of the present invention0.55Fe0.3Ni0.15)3(PO4)2SEM picture of (1);
FIG. 10 is (Fe) prepared in example 11 of the present invention0.4Mn0.2Ni0.2Mg0.2)3(PO4)2SEM picture of (1);
FIG. 11 shows LiMnPO prepared in example 26 of the present invention4SEM picture of (1);
FIG. 12 shows LiMnPO prepared in example 27 of the present invention4SEM picture of (1);
FIG. 13 is LiCoPO prepared by example 28 of the present invention4SEM picture of (1);
FIG. 14 is LiFe prepared in example 18 of the present invention0.4Mn0.6PO4SEM picture of (1);
FIG. 15 is LiFe prepared in example 19 of the present invention0.4Mn0.6PO4SEM picture of (1);
FIG. 16 is LiFe prepared in example 20 of the present invention0.4Mn0.6PO4SEM picture of (1);
FIG. 17 is LiFe prepared in example 21 of the present invention0.4Mn0.6PO4SEM picture of (1);
FIG. 18 is LiFe prepared in example 22 of the present invention0.4Mn0.6PO4SEM picture of (1);
FIG. 19 is LiFe prepared in example 23 of the present invention0.4Mn0.55Ni0.05PO4SEM picture of (1);
FIG. 20 is LiFe prepared in example 20 of the present invention0.4Mn0.6PO4A TEM image of (B);
FIG. 21 is a schematic diagram of a lithium-ion battery of the present invention;
FIG. 22 is a graph of voltage versus specific capacitance for a lithium battery prepared from the lithium metal phosphate powder of example 19 according to the present invention;
FIG. 23 is a graph of voltage versus specific capacitance for a lithium battery prepared from the lithium metal phosphate powder of example 19 in accordance with the present invention;
FIG. 24 is a graph of voltage versus specific capacitance for a lithium battery prepared from the lithium metal phosphate powder of example 20 according to the present invention.
Description of reference numerals:
11 lower cover
12 round piece
121 surface
13 isolating film
14 lithium sheet
15 shim
16 wide mouth tablet
17 upper cover
Detailed Description
In order that the objects, technical solutions and advantages of the present invention will become more apparent, the present invention will be further described in detail with reference to the accompanying drawings in conjunction with the following specific embodiments.
The present invention is described below, and those skilled in the art will appreciate that the terms used in the description are merely illustrative and not restrictive, and that the present invention may be modified and changed in accordance with the present specification. Accordingly, within the scope of the claims, the invention is not limited by the description set out in the specification.
Analysis of
The shapes of the divalent metal phosphate powder and the lithium metal phosphate powder obtained in example (Ex) below were observed with a Scanning Electron Microscope (SEM) (Hitachi S-4000).
Further, the divalent metal phosphate powder and the lithium metal phosphate powder obtained in the following examples were examined with an X-ray diffractometer (Shimadzu 6000) to analyze the crystal structures thereof. The X-ray diffraction pattern was collected with Cu Ka rays at a2 theta-scan angle of 15 deg. -45 deg., and at a scan rate of 1 deg./min. The X-ray detection standards are shown in table 1 below.
TABLE 1
| Compound (I) | Standard article |
| Mn3(PO4)2·3H2O | JCPDS No.3-426 |
| Mn3(PO4)2·7H2O | JCPDS No.84-1160 |
| Ni3(PO4)2·8H2O | JCPDS No.46-1388 or JCPDS No.1-126 |
| Co3(PO4)2·8H2O | JCPDS No.33-432 |
| Cu3(PO4)2·3H2O | JCPDS No.22-548 |
| Fe3(PO4)2·8H2O | JCPDS No.79-1928 |
| LiMnPO4 | JCPDS No.33-804 |
| LiCoPO4 | JCPDS No.85-2 |
| LiFePO4 | JCPDS No.81-1173 |
Preparation of divalent metal phosphate powder
Step I
In a molar ratio of 1: 3, adding H3PO4And NaHCO3The phosphorus precursor solution was obtained by adding 500 milliliters (ml) of deionized water, and stirred for 30 minutes.
Step II
For the preparation of Mn3(PO4)2Mixing MnSO4·5H2O is added to the phosphorus-containing precursor solution, wherein MnSO4·5H2O and H3PO4The molar ratio of (A) to (B) is 3: 2.
To prepare (Fe)1-xMnx)3(PO4)2Mixing MnSO4·5H2O and FeSO4·7H2O is added to the phosphorus-containing precursor solution, wherein MnSO4·5H2O and FeSO4·7H2Total amount of O and H3PO4In a molar ratio of 3: 2, and MnSO4·5H2O and FeSO4·7H2The molar ratio of O is as expected in Table 2 below (Fe)1-xMnx)3(PO4)2The chemical formula of (c) is adjusted.
For the production of Fe3(PO4)2FeSO is prepared4·7H2Adding O to the phosphorus-containing precursor solution, wherein FeSO47H2O and H3PO4The molar ratio of (A) to (B) is 3: 2.
For the preparation of a divalent metal phosphate powder containing at least two metals from the group consisting of Mn, Co, Ni, Cu, Cr, V, Mo, Ti, Zn, Zr, Tc, Ru, Rh, Pd, Ag, Cd, Pt, Au, Al, Ga, In, Be, Mg, Ca, Sr, B, and Nb, at least two suitable divalent metal sulfates are used, the total amount of divalent metal sulfates used and H3PO4Is 3: 2 and the molar ratio between the divalent metal sulfates used is adjusted to the divalent metal phosphate powder expected in table 2 below.
Step III
Washing the product obtained in the step II by deionized water, and centrifuging and collecting the product for three times.
Step IV
The product collected in step III was dried at 55 ℃ for 12 to 108 hours to obtain divalent metal phosphate powders as shown in Table 2 below.
The shape of the divalent metal phosphate powder was observed by SEM and examined by X-ray diffractometry. The results are shown in Table 2 below.
TABLE 2
FIG. 1 shows the present inventionMn of illustrative example 143(PO4)2SEM image of (d). FIG. 2 is Co prepared according to example 16 of the present invention3(PO4)2SEM image of (d). FIG. 3 is Cu prepared in example 17 of the present invention3(PO4)2SEM image of (d). FIG. 4 is example 3 preparation of (Mn) of the present invention0.8Fe0.1Mg0.1)3(PO4)2SEM image of (d). FIG. 5 is (Mn) prepared in example 1 of the present invention0.8Fe0.1Co0.1)3(PO4)2SEM image of (d). FIG. 6 is (Mn) prepared in example 2 of the present invention0.8Fe0.1Zn0.1)3(PO4)2SEM image of (d). FIG. 7 is (Mn) prepared in example 4 of the present invention0.8Fe0.1Ni0.1)3(PO4)2SEM image of (d). FIG. 8 is (Mn) prepared in example 5 of the present invention0.6Fe0.2Ni0.2)3(PO4)2SEM image of (d). FIG. 9 is (Mn) prepared in example 6 of the present invention0.55Fe0.3Ni0.15)3(PO4)2SEM image of (d). FIG. 10 is (Fe) prepared in example 110.4Mn0.2Ni0.2Mg0.2)3(PO4)2SEM image of (d). Fig. 1 to 10 show that most of the divalent metal phosphate powders are in the form of thin and long sheets.
In addition, MnSO is added into the phosphorus-containing precursor solution4·5H2Rate of O and Mn3(PO4)2·3H2O and Mn3(PO4)2·7H2The formation of O is relevant. If rapidly adding MnSO4·5H2O, more Mn can be obtained3(PO4)2·3H2And O. If MnSO is slowly added4·5H2O, more Mn can be obtained3(PO4)2·7H2And O. Furthermore, if the product collected in step III is dried at 55 ℃ for 12 to 108 hours, Mn cannot be completely removed3(PO4)2·7H2Water molecules of O. Therefore, to prepare the lithium metal phosphate powder, heat is first appliedThermogravimetric analysis (TGA) to calculate the water molecule content of the manganous phosphate.
Similarly, TGA was performed to calculate the water molecule content in the divalent metal phosphate for different crystals of the divalent metal phosphate with different water molecule content.
Furthermore, the rate of addition of the divalent metal sulfate to the phosphorus-containing precursor solution is also related to the thickness of the divalent metal sulfate obtained.
Preparation of lithium metal phosphate powder
Step A: ball milling step
A-1: with a divalent metal phosphate and Li3PO4Preparation of
Using a divalent metal phosphate as a precursor, mixing Li in a molar ratio of 1: 13PO4. Further, 15 wt% of a saccharide or 6.5 wt% of polystyrene was additionally added to the mixture, and mixed in a 3D mixer containing zirconia balls of 0.8mm for 2 hours to obtain a mixed powder.
A-2: with at least two divalent metal phosphates and Li3PO4Preparation of
Using at least two divalent metal phosphates as precursors, and mixing Li3PO4Wherein the total amount of divalent metal phosphate and Li3PO4The molar ratio of (A) to (B) is 1: 1. Further, 15 wt% of a saccharide or 6.5 wt% of polystyrene was additionally added to the mixture, and mixed in a 3D mixer containing zirconia balls of 0.8mm for 2 hours to obtain a mixed powder.
In one embodiment, 1 wt% of graphene oxide is further added to the mixture as a carbon source.
And B: heat treatment step
The product obtained in step A was thermally annealed at 750 ℃ for 3 hours in a nitrogen atmosphere (1 atm). Finally, the lithium metal phosphate in the form of flakes coated with carbon is obtained.
Alternatively, the heating tube may be evacuated first, then nitrogen may be introduced into the heating tube, and then the heating tube may be sealed. The product obtained in step A was heat treated in a sealed heating tube at 750 ℃ for 3 hours. The pressure during the heat treatment is kept below 1 atm. Finally, the lithium metal phosphate in the form of flakes coated with carbon is obtained.
The shape of the obtained lithium metal phosphate was observed by SEM and examined by X-ray diffractometry. The results are shown in Table 3 below.
TABLE 3
FIG. 11 shows LiMnPO prepared in example 26 of the present invention4SEM image of (d). FIG. 12 shows LiMnPO prepared in example 27 of the present invention4SEM image of (d). FIG. 13 is LiCoPO prepared by example 28 of the present invention4SEM image of (d). FIG. 14 is LiFe prepared in example 18 of the present invention0.4Mn0.6PO4SEM image of (d). FIG. 15 is LiFe prepared in example 19 of the present invention0.4Mn0.6PO4SEM image of (d). FIG. 16 is LiFe prepared in example 20 of the present invention0.4Mn0.6PO4SEM image of (d). FIG. 17 is LiFe prepared in example 21 of the present invention0.4Mn0.6PO4SEM image of (d). FIG. 18 is LiFe prepared in example 22 of the present invention0.4Mn0.6PO4SEM image of (d). FIG. 19 is LiFe prepared in example 23 of the present invention0.4Mn0.55Ni0.05PO4SEM image of (d). Fig. 11 to 19 disclose that the obtained lithium metal phosphate is in the form of a sheet having a thin thickness and a long length.
FIG. 20 is LiFe prepared in example 20 of the present invention0.4Mn0.6PO4A TEM image of (a). Fig. 20 reveals that less reduced graphene oxide exists between the sheet-like structures, and the sheet-like structures are uniformly coated with the carbon film.
According to the results of examples 1 to 17, the divalent metal phosphate powder had a small and consistent particle size. If the divalent metal phosphate powder is used as a precursor for preparing a lithium ion phosphate powder, the time of the heat treatment step can be shortened. Therefore, the cost for preparing the lithium ion battery can be further reduced. In addition, the lithium metal phosphate powder subjected to the thermal annealing treatment has a similar shape to the divalent metal phosphate powder, so that the lithium metal phosphate powder subjected to the thermal annealing also has a small and uniform particle size. Therefore, the steps of grinding and screening in the step of preparing the cathode material can be omitted, and the cost of the lithium ion battery can be reduced. In addition, according to the results of examples 18 to 29, the lithium metal phosphate powder of the present invention has a nano, micro, or sub-micro particle size. If the lithium metal phosphate powder of the present invention is used as a cathode material for a lithium ion battery, the lithium ion battery can provide stable charge and discharge current and excellent charge/discharge efficiency. Therefore, the cost of the lithium ion battery can be reduced, the charging/discharging time can be shortened, and the capacitance of the battery can be improved.
Preparation and testing of lithium ion batteries
The lithium ion battery of the present invention is prepared by a general preparation method. Briefly, PVDF, the lithium metal phosphate powders of examples 19 and 20, ZrO, KS-6[ TIMCAL ] and Super-P [ TIMCAL ] were dried in a vacuum oven for 24 hours, the lithium metal phosphate powders: PVDF: KS-6: the weight ratio of Super-P is 85: 10: 3: 2. then, the aforementioned materials were mixed in a 3D mixer containing NMP to obtain a slurry. An aluminum foil was provided and the slurry was coated by a doctor blade coating method and placed in a vacuum oven at 90 c for 12 hours. The dried aluminum foil coated with the slurry was pressed using a roller and cut into a wafer of Φ 13 mm.
Then, as shown in FIG. 21, an upper lid 17, a lower lid 11, a wide-mouthed sheet 16, a gasket 15, the above-mentioned wafer 12 having the surface 121 coated with the slurry, and a separator 13 having a diameter of 18mm were placed in a vacuum oven at 90 ℃ for drying for 24 hours, and then placed in an argon atmosphere glove box containing less than 1ppm of water and oxygen. Wetting the wafer 12 and the isolation film 13 with an electrolyte, and then wetting the wafer 12, the isolation film 13 and lithiumThe sheet 14, the gasket 15, the wide-mouthed sheet 16 and the upper cover 17 are sequentially laminated on the lower cover 11, as shown in fig. 20. After pressing and packaging, a CR2032 coin-like lithium ion battery was obtained and tested after 12-30 hours. The electrolyte used was 1M LiPF6Soluble in EC/EMC/DMC (1: 1 wt%) and 1% VC, a commonly used LiFePO4An electrolyte for a battery.
Lithium ion batteries prepared from the lithium metal phosphate powders according to examples 19 and 20 were tested using an automatic battery charge/discharge testing system (AcuTech Systems BAT-750B). FIG. 22 is a graph of voltage versus specific capacitance for a lithium ion battery prepared from the lithium metal phosphate powder of example 19 according to the present invention, which was prepared by heat treatment in a sealed nitrogen atmosphere. FIG. 23 is a graph of voltage versus specific capacitance for a lithium ion battery prepared from the lithium metal phosphate powder of example 19 according to the present invention, wherein the lithium metal phosphate powder was prepared by heat treatment in a nitrogen gas stream. Fig. 24 is a graph of voltage versus specific capacitance for a lithium ion battery prepared from the lithium metal phosphate powder of example 20 according to the present invention, wherein the lithium metal phosphate powder was prepared by heat treatment in a nitrogen gas stream.
FIGS. 22 to 24 show graphs of voltage versus specific capacitance for lithium ion batteries prepared from the lithium metal phosphate powders of examples 19 to 20 of the present invention and tested for 30 th to 40 th cycles by the same charge/discharge current (0.1C, 0.2C, 0.5C, 0.75C, and 1C). As can be seen from the results of fig. 22 to 23, the specific capacitance of the battery at a discharge current of 0.1C was about 152mAh/g, which is smaller than the specific capacitance (greater than 160mAh/g) of the lithium ion battery prepared from the lithium metal phosphate powder according to example 20 of the present invention, as shown in fig. 24. The lithium ion battery prepared from the lithium metal phosphate powder of example 19 according to the present invention can obtain an average discharge voltage of about 3.6V, which is higher than that obtained by using LiFePO4Voltage of the prepared battery (3.2-3.4V). The foregoing results show that even when using the materials commonly used for LiFePO4The energy density of the lithium ion battery prepared according to the lithium metal phosphate powder of example 19 is still higher than that of the lithium ion battery prepared with LiFePO4Energy of the prepared batteryAnd (4) measuring density.
In summary, the divalent metal phosphate powders of the present invention have a thin thickness and a high length/thickness ratio. Therefore, the time for preparing the lithium metal phosphate powder can be greatly reduced. In addition, if the obtained lithium metal phosphate powder is further applied to the preparation of a lithium ion battery, the performance of the battery can be greatly improved.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (31)
1. A divalent metal phosphate powder for use in the preparation of an electrode material for a lithium ion battery, represented by the following formula (I):
(Fe1-xMx)3(PO4)2·yH2O (I)
wherein M comprises at least one metal selected from the group consisting of Mn, Co, Ni, Cu, Cr, V, Mo, Ti, Zn, Zr, Tc, Ru, Rh, Pd, Ag, Cd, Pt, Au, Al, Ga, In, Be, Mg, Ca, Sr, B, and Nb; x is more than 0.5 and less than or equal to 1; y is an integer from 0 to 8; the divalent metal phosphate powder is composed of a plurality of flaky powders; and the length of each flake is between 50nm and 10 μm.
2. The divalent metal phosphate powder according to claim 1, wherein the flakes are individual flakes, flakes having one end of the flakes connected to each other, flakes having centers connected to each other, or flakes having one end connected to each other to form a connected center.
3. The divalent metal phosphate powder of claim 1 wherein the metal is selected from the group consisting of Mn, Co, Cu, Ni, Zn, and Mg.
4. The divalent metal phosphate powder of claim 1 wherein each flake has a thickness of between 5nm and 1 μm.
5. The divalent metal phosphate powder according to claim 1, wherein M is Mn, Co, Ni, or Cu, and 0.6. ltoreq. x.ltoreq.1.
6. The divalent metal phosphate powder according to claim 1, which is represented by the following formula (I-1):
(Fe1-x1-x2Mnx1M’x2)3(PO4)2·yH2O (I-1)
wherein M' comprises at least one metal selected from the group consisting of Co, Cu, Ni, Zn, and Mg; x1 is more than or equal to 0.2 and less than or equal to 0.8; x2 is more than or equal to 0.05 and less than or equal to 0.4; and x1+ x2 is more than 0.5 and less than or equal to 1.
7. A method of making a divalent metal phosphate powder comprising:
(a) providing a phosphorus-containing precursor solution, wherein the phosphorus-containing precursor solution comprises: a phosphorus-containing precursor and a weak base compound; and
(b) adding at least one divalent metal compound into the phosphorus-containing precursor solution to obtain divalent metal phosphate powder shown as the formula (I):
(Fe1-xMx)3(PO4)2·yH2O (I)
wherein M comprises at least one metal selected from the group consisting of Mn, Co, Ni, Cu, Cr, V, Mo, Ti, Zn, Zr, Tc, Ru, Rh, Pd, Ag, Cd, Pt, Au, Al, Ga, In, Be, Mg, Ca, Sr, B, and Nb; x is more than 0.5 and less than or equal to 1; y is an integer from 0 to 8; the divalent metal phosphate powder is composed of a plurality of flaky powders; and the length of each flake is between 50nm and 10 μm.
8. The method of claim 7, wherein the phosphorus-containing precursor is selected from the group consisting of H3PO4、NaH2PO4、Na2HPO4、Mg3(PO4)2And NH4H2PO4At least one of the group consisting of.
9. The method of claim 7, wherein the weak base compound is Na2CO3And NaHCO3At least one of (1).
10. The method of claim 7, wherein the divalent metal compound is a sulfate, carbonate, nitrate, oxalate, acetate, chlorite, bromide, or iodide of Fe, Mn, Co, Ni, Cu, Cr, V, Mo, Ti, Zn, Zr, Tc, Ru, Rh, Pd, Ag, Cd, Pt, Au, Al, Ga, In, Be, Mg, Ca, Sr, B, or Nb.
11. The method of claim 7, wherein the flakes are formed of individual flakes, flakes having one end of the flakes connected to each other, flakes having centers connected to each other, or flakes having one end connected to each other to form a connected center.
12. The method of claim 7, wherein the metal is selected from the group consisting of Mn, Co, Cu, Ni, Zn, and Mg.
13. The preparation method according to claim 7, wherein the thickness of each flake is between 5nm and 1 μm.
14. The production method according to claim 7, wherein M is Mn, Co, Ni, or Cu, and 0.6. ltoreq. x.ltoreq.1.
15. The method of claim 7, wherein the divalent metal phosphate powder is represented by the following formula (I-1):
(Fe1-x1-x2Mnx1M’x2)3(PO4)2·yH2O (I-1)
wherein M' comprises at least one metal selected from the group consisting of Co, Cu, Ni, Zn, and Mg; x1 is more than or equal to 0.2 and less than or equal to 0.8; x2 is more than or equal to 0.05 and less than or equal to 0.4; x1+ x2 is more than 0.5 and less than or equal to 1; and y is an integer of 0 to 8.
16. A lithium metal phosphate powder for a lithium ion battery, represented by the following formula (II):
LiFe1-aMaPO4 (II)
wherein M comprises at least one metal selected from the group consisting of Mn, Co, Ni, Cu, Cr, V, Mo, Ti, Zn, Zr, Tc, Ru, Rh, Pd, Ag, Cd, Pt, Au, Al, Ga, In, Be, Mg, Ca, Sr, B, and Nb; a is more than 0.5 and less than or equal to 1; the lithium metal phosphate powder is composed of a plurality of flakes; and the length of each flake is between 50nm and 10 μm.
17. The lithium metal phosphate powder of claim 16, wherein the flakes are individual flakes, flakes with one end of the flakes connected to each other, flakes with centers connected to each other, or flakes with one end connected to each other to form a connected center.
18. The lithium metal phosphate powder of claim 16, wherein the metal is selected from the group consisting of Mn, Co, Cu, Ni, Zn, and Mg.
19. The lithium metal phosphate powder of claim 16, wherein each flake has a thickness of between 5nm and 1 μm.
20. The lithium metal phosphate powder of claim 16, wherein M is Mn, Co, Ni, or Cu, and 0.6. ltoreq. a.ltoreq.1.
21. The lithium metal phosphate powder of claim 16, wherein the lithium metal phosphate powder is represented by the following formula (II-1):
LiFe1-a1-a2MnalM’a2PO4 (II-1)
wherein M' comprises at least one metal selected from the group consisting of Co, Cu, Ni, Zn, and Mg; a1 is more than or equal to 0.2 and less than or equal to 0.8; a2 is more than or equal to 0.05 and less than or equal to 0.4; and 0.5 & lt a1+ a2 & lt 1.
22. A method of preparing a lithium metal phosphate powder for a lithium ion battery, comprising:
(a) providing a divalent metal phosphate powder represented by the following formula (I):
(Fe1-xMx)3(PO4)2·yH2O (I)
wherein M comprises at least one metal selected from the group consisting of Mn, Co, Ni, Cu, Cr, V, Mo, Ti, Zn, Zr, Tc, Ru, Rh, Pd, Ag, Cd, Pt, Au, Al, Ga, In, Be, Mg, Ca, Sr, B, and Nb; x is more than 0.5 and less than or equal to 1; y is an integer from 0 to 8; the divalent metal phosphate powder is composed of a plurality of flaky powders; and the length of each flake is between 50nm and 10 μm;
(b) mixing the divalent metal phosphate powder and a lithium-containing precursor to obtain a mixed powder; and
(c) heat-treating the mixed powder to obtain a lithium metal phosphate powder represented by the formula (II):
LiFe1-aMaPO4 (Ⅱ)
wherein M comprises at least one metal selected from the group consisting of Mn, Co, Ni, Cu, Cr, V, Mo, Ti, Zn, Zr, Tc, Ru, Rh, Pd, Ag, Cd, Pt, Au, Al, Ga, In, Be, Mg, Ca, Sr, B, and Nb; a is more than 0.5 and less than or equal to 1; the lithium metal phosphate powder is composed of a plurality of flakes; and the length of each flake is between 50nm and 10 μm.
23. The method of claim 22, wherein the step (a) comprises the steps of:
(a1) providing a phosphorus-containing precursor solution, wherein the phosphorus-containing precursor solution comprises: a phosphorus-containing precursor and a weak base compound; and
(a2) adding at least one divalent metal compound into the phosphorus-containing precursor solution to obtain divalent metal phosphate powder shown in the formula (I).
24. The method of claim 23, wherein the phosphorus-containing precursor is selected from the group consisting of H3PO4、NaH2PO4、Na2HPO4、Mg3(PO4)2And NH4H2PO4At least one of the group consisting of.
25. The method of claim 23, wherein the weak base compound Na2CO3And NaHCO3At least one of (1).
26. The method of claim 23, wherein the divalent metal compound is a sulfate, carbonate, nitrate, oxalate, acetate, chlorite, bromide, or iodide of Fe, Mn, Co, Ni, Cu, Cr, V, Mo, Ti, Zn, Zr, Tc, Ru, Rh, Pd, Ag, Cd, Pt, Au, Al, Ga, In, Be, Mg, Ca, Sr, B, or Nb.
27. The method of claim 22, wherein the lithium-containing precursor is selected from the group consisting of LiOH, Li2CO3、LiNO3、CH3COOLi、Li2C2O4、Li2SO4、LiCl、LiBr、LiI、LiH2PO4、Li2HPO4And Li3PO4At least one of the group consisting of.
28. The method of claim 22, wherein the step (b) comprises mixing the divalent metal phosphate powder with the lithium precursor and at least one carbon-containing material to obtain the mixed powder.
29. The method of claim 28, wherein the carbon-containing material is a carbohydrate, stearic acid, citric acid, lauric acid, polystyrene spheres, graphene oxide, or vitamin C.
30. The method according to claim 22, wherein the step (c) is performed by heat-treating the mixed powder under an atmosphere, in a vacuum or under an introduced gas flow.
31. The method of claim 30, wherein the atmosphere or the introduced gas stream is selected from the group consisting of N2、H2He, Ne, Ar, Kr, Xe, CO, methane, Ar-H2And N2-H2At least one of the group consisting of mixed gases.
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| CN110635132B (en) | 2021-10-15 |
| TW202002368A (en) | 2020-01-01 |
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