CN114497452A - Positive electrode material for silicon battery and preparation method and application thereof - Google Patents
Positive electrode material for silicon battery and preparation method and application thereof Download PDFInfo
- Publication number
- CN114497452A CN114497452A CN202111631608.0A CN202111631608A CN114497452A CN 114497452 A CN114497452 A CN 114497452A CN 202111631608 A CN202111631608 A CN 202111631608A CN 114497452 A CN114497452 A CN 114497452A
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- lithium
- salt
- silicon
- electrode material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a positive electrode material for a silicon battery, a preparation method and application thereof, wherein the chemical formula of the positive electrode material is Li1+aNibMncMc‑dO2Wherein a is more than or equal to 0 and less than or equal to 1, b is more than 0 and less than 1, c is more than 0 and less than 1, d is more than or equal to c, and b +2c-d is less than 1+ a; m is at least one of Ti, Zr, La, Ce, Pr, Nd, Nb, Sm, Al, Mg, Sr, Ba, Co, Zn, Sn, Bi, Sb, Si, Tb, Bi, Yb, Lu, B and Y. Compared with the prior art, the positive electrode material provided by the invention carries a part of lithium, can be used for generating lithium which needs to be consumed by an SEI (solid electrolyte interface) film in the first charging process of a silicon negative electrode material, and solves the problems that the prior silicon lithium ion battery needs to be pre-lithiated in advance and has high production costThe matching with the silicon-based anode material is higher.
Description
Technical Field
The invention relates to the field of lithium batteries, in particular to a positive electrode material for a silicon battery, and a preparation method and application thereof.
Background
The lithium ion battery is a secondary battery with wide application, and with the pursuit of the lithium ion battery for high energy density, particularly for the power battery to achieve the specific energy target of 300Wh/kg of a single body, the negative electrode material must be silicon (nano silicon or silicon oxide and the like) negative electrode. However, the silicon-based negative electrode material has a fatal problem that a solid electrolyte membrane (SEI film) is generated at the time of initial lithium intercalation reaction, and a part of lithium is consumed in the process. When the conventional positive electrode material is matched with a silicon negative electrode, a large amount of active lithium extracted from the positive electrode material in the first charging process becomes dead lithium and is confined in an SEI (solid electrolyte interphase) film of the silicon negative electrode, so that the actual specific energy of the battery is greatly reduced.
In order to solve the problem, lithium is supplemented in the silicon negative electrode lithium ion battery through pre-lithiation, and lithium consumed by an SEI (solid electrolyte interphase) film generated by the silicon negative electrode is compensated. At present, two types of pre-lithiation methods are reported, namely lithium is supplemented at the positive end or lithium is supplemented at the negative end.
The conventional positive pole end lithium supplement technology is mainly characterized in that some compounds with high lithium content and capable of being extracted, such as Li, are added in the process of preparing positive pole piece slurry2O、Li2NiO2And Li5FeO4And (4) class. The compounds with higher lithium content are generally sensitive to moisture in air, so that strict requirements are made on moisture control of a slurry preparation environment and a pole piece coating environment, the humidity environment of the existing battery production line needs to be upgraded and modified, and the modification cost is high.
The conventional negative electrode end lithium supplement technology generally combines lithium foil, lithium strips, metal lithium powder and the like with the preparation process of a negative electrode plate to realize lithium supplement. Lithium foil, lithium strips, lithium metal powder and the like are relatively active, have strict requirements on environmental humidity, atmosphere and the like, and are easy to cause safety accidents such as fire or explosion without attention. And therefore, higher demands are made on equipment and environment of a battery production plant.
For lithium ion battery production enterprises, the two lithium supplement modes increase the technical difficulty, the existing production equipment needs to be improved or upgraded, and the production cost is increased.
In view of the above, it is necessary to provide a technical solution to the above problems.
Disclosure of Invention
One of the objects of the present invention is: the invention provides a positive electrode material for a silicon-based battery, which aims to solve the problems of high technical difficulty and high production cost of pre-lithiation in the conventional silicon-based lithium ion battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
a positive electrode material for silicon battery with chemical formula of Li1+aNibMncMc-dO2Wherein a is more than or equal to 0 and less than or equal to 1, b is more than 0 and less than 1, c is more than 0 and less than 1, d is more than or equal to c, and b +2c-d is less than 1+ a; m is at least one of Ti, Zr, La, Ce, Pr, Nd, Nb, Sm, Al, Mg, Sr, Ba, Co, Zn, Sn, Bi, Sb, Si, Tb, Bi, Yb, Lu, B and Y.
Another object of the present invention is to provide a method for preparing the positive electrode material for a silicon-based battery, including the steps of:
s1, mixing nickel salt and manganese salt to prepare a first solution, adding the first solution and an alkaline solution into a reactor respectively in an inert gas, stirring and reacting, and controlling the pH value of the solution to be 7-13; continuously stirring and aging for 18-26 h after feeding, carrying out vacuum filtration, washing and drying to obtain a precursor;
s2, mixing the precursor obtained in the step S1 with lithium salt, loading the mixture into a reaction furnace, reacting for 8-30 hours at 450-900 ℃, cooling, and grinding to obtain the positive electrode material for the silicon battery;
wherein, the M salt is mixed with the nickel salt and the manganese salt to prepare a first solution in step S1, or is mixed with the precursor and the lithium salt obtained in step S1 to react in step S2.
Preferably, the lithium salt is at least one of lithium oxide, lithium carbonate, lithium nitrate, lithium acetate and lithium hydroxide; the nickel salt is at least one of nitrate of nickel, carbonate of nickel, nickel oxalate, nickel acetate and nickel oxide; the manganese salt is at least one of nitrate of manganese, carbonate of manganese, manganese oxalate, manganese acetate and manganese oxide; the M salt is at least one of nitrate of M, carbonate of M, acetate of M, hydroxide of M and oxide of M.
Preferably, the nickel, manganese and M in the nickel, manganese and M salts are represented as metal a, and the molar ratio of the metal a to the lithium in the lithium salt is 1: (1.05-1.5).
Preferably, in step S1, the precursor is prepared by: mixing nickel salt, manganese salt and M salt to prepare a first solution, adding the first solution and an alkaline solution into a reactor with deionized water at the speed of 0.8-1.2 mL/min respectively at the temperature of 30-80 ℃ in inert gas, stirring for reaction at the speed of 400-600 rpm/min, and controlling the pH value of the solution to be 7-13; and after feeding, continuously stirring and aging for 18-26 h, carrying out vacuum filtration, washing, and drying at 100-120 ℃ for 40-60 h to obtain a precursor.
Preferably, in step S2, the lithium salt is divided into a first part and a second part, the first part of lithium salt is mixed with the precursor, the mixture is reacted at 450 to 900 ℃ for 8 to 24 hours, and the mixture is cooled and ground; and then adding a second part of lithium salt, mixing, reacting for 8-24 h at 450-900 ℃, cooling, and grinding to obtain the positive electrode material for the silicon battery.
Preferably, the mass ratio of the first lithium salt to the second lithium salt is (5-9): (5-1).
Preferably, in step S2, mixing the first part of lithium salt with the precursor, heating to 450-650 ℃ at a rate of 4-7 ℃/min, holding the temperature for 1-3 h, heating to 700-900 ℃ at a rate of 4-7 ℃/min, holding the temperature for 10-24 h, cooling, and grinding; and then adding a second part of lithium salt, mixing, heating to 450-650 ℃ at the speed of 4-7 ℃/min, preserving heat for 1-3 h, heating to 700-900 ℃ at the speed of 4-7 ℃/min, preserving heat for 10-24 h, cooling, and grinding to obtain the positive electrode material for the silicon battery.
The present invention also provides a positive electrode sheet comprising a positive electrode current collector and a positive electrode active material layer coated on at least one surface of the positive electrode current collector, wherein the positive electrode active material layer comprises the positive electrode material for silicon batteries.
The invention also provides a lithium ion battery, which comprises a positive plate, a negative plate and a diaphragm arranged between the positive plate and the negative plate, wherein the negative active material in the negative plate is a silicon material, and the positive plate is the positive plate.
Compared with the prior art, the invention has the beneficial effects that:
1) the positive electrode material for the silicon-based lithium ion battery provided by the invention is provided with a part of lithium, and the lithium cannot be embedded into the material again after being firstly extracted (corresponding to the first charging process), so the positive electrode material is matched with the silicon-based negative electrode material for use, can be used for generating lithium which needs to be consumed by an SEI (solid electrolyte interface) film in the first charging process of the silicon-based negative electrode material, and compared with the method that a pre-lithiation process needs to be added when other positive electrode materials are matched with the silicon-based negative electrode material, the positive electrode material avoids the process of additionally adding a lithium supplement agent, reduces the process complexity and the production difficulty of the production process of the battery, solves the problems that the prior silicon-based lithium ion battery needs to be pre-lithiated in advance and the production cost is high, and is higher in matching with the silicon-based negative electrode material.
2) In addition, the cathode material provided by the invention has higher specific capacity, and even if part of lithium ions are released during the first charging to form an SEI film for the silicon-based cathode, the cathode material can still be matched with the high-capacity silicon-carbon-based cathode and provide higher specific capacity.
3) In addition, the preparation method provided by the invention can effectively adjust the surplus lithium amount (for the silicon-carbon negative electrode to form an SEI film) and the effective specific mass capacity (the specific mass capacity which can be recovered after the first discharge) in the positive electrode material for the silicon battery, thereby matching with different types of silicon negative electrode materials.
Drawings
Fig. 1 is an XRD chart of the positive electrode material for a silicon-based battery of example 1 of the present invention.
Fig. 2 is an XRD chart of the positive electrode material for silicon-based battery of example 2 of the present invention.
Fig. 3 is an XRD chart of the positive electrode material for silicon-based battery of example 3 of the present invention.
Fig. 4 is an XRD chart of the positive electrode material for silicon-based battery of example 6 of the present invention.
Fig. 5 is an XRD chart of the positive electrode material for silicon-based battery of example 9 of the present invention.
Detailed Description
1. Positive electrode material for silicon-based battery
The first aspect of the present invention provides a positive electrode material for a silicon-based battery, which has a chemical formula of Li1+aNibMncMc-dO2Wherein a is more than or equal to 0 and less than or equal to 1, b is more than 0 and less than 1, c is more than 0 and less than 1, d is more than or equal to c, and b +2c-d is less than 1+ a; m is at least one of Ti, Zr, La, Ce, Pr, Nd, Nb, Sm, Al, Mg, Sr, Ba, Co, Zn, Sn, Bi, Sb, Si, Tb, Bi, Yb, Lu, B and Y.
Specifically, the positive electrode material for silicon-based batteries of the present invention includes, but is not limited to
Li1.05Ni0.8Mn0.1Co0.05Al0.05O2、Li1.05Ni0.8Mn0.1Co0.05Mg0.05O2、Li1.05Ni0.8Mn0.1Co0.05Ti0.05O2、Li1.05Ni0.6Mn0.35Co0.05O2、Li1.12Ni0.8Mn0.1Co0.05Al0.05O2、Li1.12Ni0.8Mn0.1Co0.05Mg0.05O2、Li1.12Ni0.8Mn0.1Co0.05Ti0.05O2、Li1.12Ni0.8Mn0.1Co0.05Ce0.05O2、Li1.12Ni0.8Mn0.1Co0.05Yb0.05O2、Li1.2Ni0.6Mn0.35Co0.05O2、Li1.25Ni0.6Mn0.3Co0.05Al0.05O2、Li1.25Ni0.6Mn0.3Co0.05Mg0.05O2、Li1.25Ni0.6Mn0.3Co0.05Ce0.05O2、Li1.3Ni0.6Mn0.3Co0.05Al0.05O2。
The positive electrode material provided by the invention solves the problems that a lithium ion battery taking a silicon material as a negative electrode needs additional lithium supplement and needs to be matched with a high-capacity positive electrode material in a one-stop manner.
The second aspect of the invention provides a preparation method of the positive electrode material for the silicon battery, which comprises the following steps:
s1, mixing nickel salt, manganese salt and M salt to prepare a first solution, adding the first solution and an alkaline solution into a reactor respectively in inert gas, stirring and reacting, and controlling the pH value of the solution to be 7-13; continuously stirring and aging for 18-26 h after feeding, carrying out vacuum filtration, washing and drying to obtain a precursor;
and S2, mixing the precursor obtained in the step S1 with lithium salt, loading the mixture into a reaction furnace, reacting for 8-24 hours at 450-900 ℃, cooling, and grinding to obtain the positive electrode material for the silicon battery.
The second aspect of the invention provides another preparation method of the positive electrode material for the silicon battery, which comprises the following steps:
s1, mixing nickel salt and manganese salt to prepare a first solution, adding the first solution and an alkaline solution into a reactor respectively in an inert gas, stirring and reacting, and controlling the pH value of the solution to be 7-13; continuously stirring and aging for 18-26 h after feeding, carrying out vacuum filtration, washing and drying to obtain a precursor;
and S2, mixing the precursor obtained in the step S1 with M salt and lithium salt, putting the mixture into a reaction furnace, reacting for 8-24 hours at 450-900 ℃, cooling, and grinding to obtain the positive electrode material for the silicon battery.
The preparation method provided by the invention comprises the steps of firstly preparing a hydroxide type or carbonate type nickel-manganese precursor, then mixing the precursor with lithium salt (or lithium salt and M salt), and reacting to obtain the lithium-rich nickel-manganese anode material for the silicon battery. Compared with the conventional method for preparing the cathode material by mixing, on one hand, the method can obtain the lithium-nickel-manganese-rich cathode material, can effectively ensure the integral specific capacity of the cathode material, and can bring part of irreversible lithium to be used for generating an SEI film in the primary charging process; on the other hand, the method has good compatibility with the existing preparation method of the anode material, does not need to additionally increase equipment, does not need production investment such as environmental control and the like, and saves the production cost of the battery.
In some embodiments, the lithium salt is at least one of lithium oxide, lithium carbonate, lithium nitrate, lithium acetate, and lithium hydroxide; the nickel salt is at least one of nitrate of nickel, carbonate of nickel, nickel oxalate and nickel oxide; the manganese salt is at least one of nitrate of manganese, carbonate of manganese, manganese oxalate and manganese oxide; the M salt is at least one of nitrate of M, carbonate of M, acetate of M, hydroxide of M and oxide of M.
In some embodiments, the nickel, manganese and M in the nickel, manganese and M salts are represented as metal a, and the molar ratio of the metal a to the lithium in the lithium salt is 1: (1.05-1.5). The molar amount of the metal A is the molar amount of all the metals added, namely the molar amount of the metals nickel, manganese and M and the molar amount of lithium are in a ratio of 1: (1.05-1.5). Specifically, the molar ratio of the two may be 1:1.05, 1:1.1, 1:1.12, 1:1.15, 1:1.18, 1:1.2, 1:1.22, 1:1.25, 1:1.3, 1:1.4 or 1: 1.5. The positive electrode material is a lithium-rich positive electrode material, so that a part of irreversible lithium carried by the obtained positive electrode material can be ensured to be used for generating an SEI (solid electrolyte interphase) film in the first charging process, and a large amount of effective specific mass capacity is still used for being matched with a high-capacity silicon negative electrode material.
In some embodiments, in step S1, the precursor is prepared by: mixing nickel salt, manganese salt and M salt to prepare a first solution, adding the first solution and an alkaline solution into a reactor with deionized water at the speed of 0.8-1.2 mL/min respectively at the temperature of 30-80 ℃ in inert gas, stirring for reaction at the speed of 400-600 rpm/min, and controlling the pH value of the solution to be 7-13; and after feeding, continuously stirring and aging for 18-26 h, carrying out vacuum filtration, washing, and drying at 100-120 ℃ for 40-60 h to obtain a precursor.
In some embodiments, in step S2, the lithium salt is first divided into a first part and a second part, the first part of lithium salt is mixed with the precursor, reacted at 450-900 ℃ for 8-24 h, cooled, and ground; and then adding a second part of lithium salt, mixing, reacting for 8-24 h at 450-900 ℃, cooling, and grinding to obtain the positive electrode material for the silicon battery.
In some embodiments, the mass ratio of the first portion of lithium salt to the second portion of lithium salt is (5-9): (5-1). By adopting the method of adding lithium salt in a distributed manner, the proportion of the surplus lithium capacity (for the silicon-carbon negative electrode to form an SEI film) and the effective specific mass capacity (the specific mass capacity which can be recovered after the first discharge) of the positive electrode material can be adjusted so as to better match the application of the silicon-based lithium ion battery. Specifically, the mass ratio of the first portion of lithium salt to the second portion of lithium salt may be 5:5, 6:4, 7:3, 8:2, or 9: 1. Preferably, the mass ratio of the first portion of lithium salt to the second portion of lithium salt is 5:5, 6:4, 7:3, or 8: 2.
In some embodiments, in step S2, the first part of lithium salt is mixed with the precursor, the temperature is raised to 450-650 ℃ at a rate of 4-7 ℃/min, the temperature is maintained for 1-3 h, the temperature is raised to 700-900 ℃ at a rate of 4-7 ℃/min, the temperature is maintained for 10-24 h, and then the mixture is cooled and ground; and then adding a second part of lithium salt, mixing, heating to 450-650 ℃ at the speed of 4-7 ℃/min, preserving heat for 1-3 h, heating to 700-900 ℃ at the speed of 4-7 ℃/min, preserving heat for 10-24 h, cooling, and grinding to obtain the positive electrode material for the silicon battery.
2. Positive plate
The invention provides a positive plate, which comprises a positive current collector and a positive active material layer coated on at least one surface of the positive current collector, wherein the positive active material layer comprises the positive material for the silicon battery.
3. Lithium ion battery
The invention provides a lithium ion battery, which comprises a positive plate, a negative plate and a diaphragm arranged between the positive plate and the negative plate, wherein a negative active substance in the negative plate is a silicon material, and the positive plate is the positive plate.
Wherein, the silicon material can be selected from one or more of silicon oxide, silicon-carbon compound and silicon alloy.
In order to make the technical solutions and advantages of the present invention clearer, the present invention and its advantages will be described in further detail below with reference to the following detailed description and the accompanying drawings, but the embodiments of the present invention are not limited thereto.
Example 1
A positive electrode material for silicon battery with chemical formula of Li1.05Ni0.8Mn0.1Co0.05Al0.05O2。
The preparation method of the anode material for the silicon battery comprises the following steps:
s1, preparing NiSO according to the molar ratio of 8:1:0.5:0.54、MnSO4、CoSO4、(Al)2(SO4)3Aqueous solution of (Ni)2+、Mn2 +、Co2+、Al3+Total concentration of (2 mol L)-1)500mL, and is marked as a first solution; 4mol of L are prepared-1500mL of NaOH solution is used as alkaline solution; adding the first solution and the alkaline solution into a five-neck flask reactor with 100mL of deionized water at the speed of about 1mL/min by a peristaltic pump at the temperature of 30-80 ℃ in an inert gas, stirring for reaction at the speed of 500rpm/min, and dropwise adding ammonia water to control the pH value of the solution to be 10-13 in the reaction process; continuously stirring and aging for 24 hours after feeding; after aging, the obtained precipitate was vacuum filtered, washed with deionized water several times, and dried in a vacuum drying oven at 110 deg.C for 48h to obtain a precursor (Ni)0.8Mn0.1Co0.05Al0.05)(OH)2。
S2, mixing the precursor (Ni)0.8Mn0.1Co0.05Al0.05)(OH)2With LiOH. H2O (Metal)Mole of a to Li is 1: 1.05) mechanically mixing, putting the mixture into a sagger, putting the sagger into a muffle furnace, taking oxygen as sintering atmosphere, raising the temperature to 450 ℃ at the speed of 6 ℃/min, and preserving the temperature for 2 hours; then raising the temperature to 760 ℃ at the speed of 6 ℃/min, and preserving the temperature for 12 h; cooling to room temperature along with the furnace and grinding to obtain the anode material Li for the silicon battery1.05Ni0.8Mn0.1Co0.05Al0.05O2。
Example 2
A positive electrode material for silicon battery with chemical formula of Li1.05Ni0.6Mn0.35Co0.05O2。
The preparation method of the anode material for the silicon battery comprises the following steps:
s1, preparing NiSO according to the ratio of 6:3.5:0.54、MnSO4、CoSO4Aqueous solution of (Ni)2+、Mn2+、Co2+Total concentration of (2 mol L)-1)500mL, and is marked as a first solution; 4mol of L are prepared-1500mL of NaOH solution is used as alkaline solution; adding the first solution and the alkaline solution into a five-neck flask reactor with 100mL of deionized water at the speed of about 1mL/min by a peristaltic pump at the temperature of 30-80 ℃ in an inert gas, stirring for reaction at the speed of 500rpm/min, and dropwise adding ammonia water to control the pH value of the solution to be 10-13 in the reaction process; continuously stirring and aging for 24 hours after feeding; after aging, the obtained precipitate was vacuum filtered, washed with deionized water several times, and dried in a vacuum drying oven at 110 deg.C for 48h to obtain a precursor (Ni)0.6Mn0.35Co0.05)(OH)2。
S2, mixing the precursor (Ni)0.6Mn0.35Co0.05)(OH)2With Li2CO3Mechanically mixing (molar ratio of metal A to Li is 1: 1.05), loading the mixture into a sagger, putting the sagger into a muffle furnace, taking oxygen as sintering atmosphere, raising the temperature to 650 ℃ at the speed of 6 ℃/min, and preserving the temperature for 2 h; then heating to 840 ℃ at the speed of 6 ℃/min, and preserving the heat for 12 h; cooling to room temperature along with the furnace and grinding to obtain the anode material Li for the silicon battery1.05Ni0.6Mn0.35Co0.05O2。
Example 3
The difference from embodiment 1 is step S2.
S2, weighing the precursor (Ni)0.8Mn0.1Co0.05Al0.05)(OH)2With LiOH. H2O (molar ratio of metal A to Li is 1: 1.12), and reacting with LiOH. H2O is divided into 7:3 parts according to the mass ratio; firstly, the precursor is mixed with 70 percent of LiOH H2Mechanically mixing O, putting the mixture into a sagger, putting the sagger into a muffle furnace, taking oxygen as sintering atmosphere, heating to 450 ℃ at the speed of 6 ℃/min, and preserving heat for 2 hours; then raising the temperature to 760 ℃ at the speed of 6 ℃/min, and preserving the temperature for 12 h; cooling to room temperature along with the furnace and then grinding; then adding LiOH & H accounting for 30 percent of the total weight2Mixing O, heating to 450 ℃ at the speed of 6 ℃/min, and keeping the temperature for 2 h; then heating to 700 ℃ at the speed of 6 ℃/min, and preserving heat for 12 h; cooling to room temperature along with the furnace and then grinding; obtaining the positive electrode material Li for the silicon battery1.12Ni0.8Mn0.1Co0.05Al0.05O2。
The rest is the same as embodiment 1, and the description is omitted here.
Example 4
The difference from example 3 is that the lithium salt is added in step S2 in the order of the first addition of 80% lithium salt and the second addition of 20% lithium salt.
The rest is the same as embodiment 3, and the description is omitted here.
Example 5
The difference from example 3 is that the lithium salt is added in step S2 in the order of 50% lithium salt in the first addition and 50% lithium salt in the second addition.
The rest is the same as embodiment 3, and the description is omitted here.
Example 6
The difference from embodiment 2 is step S2.
S2, weighing the precursor (Ni)0.6Mn0.35Co0.05)(OH)2With Li2CO3(molar ratio of metal A to Li 1: 1.2), and mixing Li with the mixture2CO3The weight ratio of the raw materials is 8: 2;firstly, the precursor is mixed with 80 percent of Li2CO3Mechanically mixing, placing the mixture into a sagger, placing into a muffle furnace, taking oxygen as sintering atmosphere, heating to 650 ℃ at the speed of 6 ℃/min, and keeping the temperature for 2 h; then heating to 840 ℃ at the speed of 6 ℃/min, and preserving the heat for 12 h; cooling to room temperature along with the furnace and then grinding; then adding Li in 20%2CO3Mixing, heating to 450 deg.C at a rate of 6 deg.C/min, and maintaining for 2 hr; then heating to 820 ℃ at the speed of 6 ℃/min, and preserving heat for 12 h; cooling to room temperature along with the furnace and then grinding; obtaining the positive electrode material Li for the silicon battery1.12Ni0.8Mn0.1Co0.05Al0.05O2。
The rest is the same as embodiment 2, and the description is omitted here.
Example 7
The difference from example 6 is that the lithium salts were sequentially added in the step S2 in a ratio of 90% lithium salt in the first addition and 10% lithium salt in the second addition.
The rest is the same as embodiment 6, and the description is omitted here.
Example 8
The difference from example 6 is that the lithium salt was added in the step S2 in the order of the first addition of 50% lithium salt and the second addition of 50% lithium salt.
The rest is the same as embodiment 6, and the description is omitted here.
Example 9
A positive electrode material for silicon battery with chemical formula of Li1.25Ni0.6Mn0.3Co0.05Al0.05O2。
The preparation method of the anode material for the silicon battery comprises the following steps:
s1, preparing NiSO according to the ratio of 6:3:0.54、MnSO4、CoSO4Aqueous solution of (Ni)2+、Mn2+、Co2+Total concentration of (2 mol L)-1)500mL, and is marked as a first solution; 4mol of L are prepared-1500mL of NaOH solution is used as alkaline solution; passing the first solution and the alkaline solution through a peristaltic pump at a temperature of about 1mL/min in an inert gas at 30-80 deg.CAdding the mixture into a five-mouth flask reactor containing 100mL of deionized water, stirring for reaction at the speed of 500rpm/min, and dropwise adding ammonia water to control the pH value of the solution to be 10-13 in the reaction process; continuously stirring and aging for 24 hours after feeding; after aging, the obtained precipitate was vacuum filtered, washed with deionized water several times, and dried in a vacuum drying oven at 110 deg.C for 48h to obtain a precursor (Ni)0.6Mn0.3Co0.05)(OH)2。
S2, weighing the precursor (Ni)0.6Mn0.3Co0.05)(OH)2With Li2CO3(molar ratio of metal A to Li 1: 1.25), and mixing Li with the mixture2CO3The weight ratio of the raw materials is 8: 2; firstly, the precursor is mixed with 80 percent of Li2CO3Mechanically mixing, placing the mixture into a sagger, placing into a muffle furnace, taking oxygen as sintering atmosphere, heating to 650 ℃ at the speed of 6 ℃/min, and keeping the temperature for 2 h; then heating to 840 ℃ at the speed of 6 ℃/min, and preserving the heat for 12 h; cooling to room temperature along with the furnace and then grinding; then adding Al (OH)3And 20% by weight of Li2CO3Mixing, heating to 450 deg.C at a rate of 6 deg.C/min, and maintaining for 2 hr; then heating to 820 ℃ at the speed of 6 ℃/min, and preserving heat for 12 h; cooling to room temperature along with the furnace and then grinding; obtaining the positive electrode material Li for the silicon battery1.25Ni0.6Mn0.3Co0.05Al0.05O2。
When XRD was measured on the positive electrode materials for silicon batteries obtained in examples 1 to 3, 6 and 9, as shown in FIGS. 1 to 5, it can be seen that Li, a positive electrode material for silicon batteries, was successfully prepared in the present invention1+aNibMncMc-dO2。
The positive electrode materials for silicon batteries obtained in examples 1 to 9 were applied to a positive electrode sheet, and the positive electrode sheet was prepared by mixing and slurrying an active material (i.e., the positive electrode material for silicon batteries), super P, and a PVDF binder.
The obtained positive plate is applied to a button cell to test performance, the adopted counter electrode is a metal lithium plate, and the electrolyte is 1mol/L LiPF6EC, DMC, EMC (volume ratio 1: 1): 1) the solution and the membrane are celgard2400 polypropylene membranes. In the test process, the highest cut-off voltage of the examples 1 and 3 to 5 was 4.2V, the highest cut-off voltage of the examples 2 and 6 to 9 was 4.4V, and the first charge and discharge current was 0.1C.
In addition, the obtained positive plate is prepared into a full cell and tested for performance, silicon carbon is used as a negative electrode material, and the electrolyte is 1mol/L LiPF6The separator is a celgard2400 polypropylene film, and a soft package full cell (404050) is prepared from the EC, DMC and EMC (volume ratio is 1: 1: 1) solutions. In the test process, the highest cut-off voltage of the examples 1 and 3 to 5 was 4.2V, the highest cut-off voltage of the examples 2 and 6 to 9 was 4.4V, the first charge and discharge current was 0.1C, and the cyclic charge and discharge current was 1C.
The test results are shown in table 1 below.
TABLE 1
From the test results, the positive electrode material Li for the silicon battery obtained by the preparation method of the invention1+ aNibMncMc-dO2And a part of irreversible lithium carried by the lithium ion battery can be used for generating an SEI film in the first charging process, and meanwhile, the effective mass specific capacity is higher, and the lithium ion battery can be well matched with a silicon negative electrode material, so that the lithium ion battery formed by the positive electrode material and the silicon negative electrode material does not need additional lithium supplement, the preparation process is simple, the production cost is low, and the problems of high pre-lithiation technical difficulty and high production cost in the conventional silicon lithium ion battery are solved.
In addition, as can be seen from the comparison among examples 1, 3 to 5, and 2, 6 to 8, when the preparation method of adding lithium salts in a distributed manner is adopted, the ratio of the surplus lithium amount (for the silicon-carbon negative electrode to form the SEI film) to the effective specific mass capacity (the specific mass capacity which can be recovered after the first discharge) of the positive electrode material can be adjusted, so that the irreversible capacity of the positive electrode material can be improved, and more lithium salts can be applied to the generation of the SEI film, so as to ensure the subsequent cycle performance. Preferably, when the mass ratio of the lithium salt added in the two parts is 5: 5-8: 2, the irreversible capacity is effectively increased, and the excellent capacity retention rate can be maintained after 500 weeks of circulation.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (10)
1. A positive electrode material for a silicon battery, characterized in that it has a chemical formula of Li1+aNibMncMc-dO2Wherein a is more than or equal to 0 and less than or equal to 1, b is more than 0 and less than 1, c is more than 0 and less than 1, d is more than or equal to c, and b +2c-d is less than 1+ a; m is at least one of Ti, Zr, La, Ce, Pr, Nd, Nb, Sm, Al, Mg, Sr, Ba, Co, Zn, Sn, Bi, Sb, Si, Tb, Bi, Yb, Lu, B and Y.
2. A method for producing the positive electrode material for a silicon-based battery according to claim 1, comprising the steps of:
s1, mixing nickel salt and manganese salt to prepare a first solution, adding the first solution and an alkaline solution into a reactor respectively in an inert gas, stirring and reacting, and controlling the pH value of the solution to be 7-13; continuously stirring and aging for 18-26 h after feeding, carrying out vacuum filtration, washing and drying to obtain a precursor;
s2, mixing the precursor obtained in the step S1 with lithium salt, loading the mixture into a reaction furnace, reacting for 8-24 hours at 450-900 ℃, cooling and grinding to obtain the positive electrode material for the silicon battery;
wherein, the M salt is mixed with the nickel salt and the manganese salt to prepare a first solution in step S1, or is mixed with the precursor and the lithium salt obtained in step S1 to react in step S2.
3. The method for producing a positive electrode material for a silicon-based battery according to claim 2, wherein the lithium salt is at least one of lithium oxide, lithium carbonate, lithium nitrate, lithium acetate, and lithium hydroxide; the nickel salt is at least one of nitrate of nickel, carbonate of nickel, nickel oxalate, nickel acetate and nickel oxide; the manganese salt is at least one of nitrate of manganese, carbonate of manganese, manganese oxalate, manganese acetate and manganese oxide; the M salt is at least one of nitrate of M, carbonate of M, acetate of M, hydroxide of M and oxide of M.
4. The method of claim 2, wherein nickel, manganese, and M in the nickel salt, manganese salt, and M salt are represented as a metal a, and a molar ratio of the metal a to lithium in the lithium salt is 1: (1.05-1.5).
5. The method of manufacturing a positive electrode material for a silicon-based battery according to claim 2, wherein the precursor is manufactured in step S1 by: mixing nickel salt, manganese salt and M salt to prepare a first solution, adding the first solution and an alkaline solution into a reactor with deionized water at the speed of 0.8-1.2 mL/min respectively at the temperature of 30-80 ℃ in inert gas, stirring for reaction at the speed of 400-600 rpm/min, and controlling the pH value of the solution to be 7-13; and after feeding, continuously stirring and aging for 18-26 h, carrying out vacuum filtration, washing, and drying at 100-120 ℃ for 40-60 h to obtain a precursor.
6. The method of claim 2 or 5, wherein in step S2, the lithium salt is divided into a first part and a second part, the first part of lithium salt is mixed with the precursor, and the mixture is reacted at 450-900 ℃ for 8-24 h, cooled and ground; and then adding a second part of lithium salt, mixing, reacting for 8-24 h at 450-900 ℃, cooling, and grinding to obtain the positive electrode material for the silicon battery.
7. The method for producing the positive electrode material for a silicon-based battery according to claim 6, wherein the mass ratio of the first lithium salt to the second lithium salt is (5-9): (5-1).
8. The method for preparing the positive electrode material for the silicon-based battery according to claim 7, wherein in step S2, the first part of lithium salt is mixed with the precursor, the temperature is raised to 450-650 ℃ at a rate of 4-7 ℃/min, the temperature is maintained for 1-3 h, the temperature is raised to 700-900 ℃ at a rate of 4-7 ℃/min, the temperature is maintained for 10-24 h, and then the mixture is cooled and ground; and then adding a second part of lithium salt, mixing, heating to 450-650 ℃ at the speed of 4-7 ℃/min, preserving heat for 1-3 h, heating to 700-900 ℃ at the speed of 4-7 ℃/min, preserving heat for 10-24 h, cooling, and grinding to obtain the positive electrode material for the silicon battery.
9. A positive electrode sheet comprising a positive electrode current collector and a positive electrode active material layer coated on at least one surface of the positive electrode current collector, wherein the positive electrode active material layer comprises the positive electrode material for a silicon-based battery according to claim 1.
10. A lithium ion battery comprising a positive plate, a negative plate and a separator interposed between the positive plate and the negative plate, wherein the negative active material in the negative plate is a silicon-based material, and the positive plate is the positive plate according to claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111631608.0A CN114497452A (en) | 2021-12-28 | 2021-12-28 | Positive electrode material for silicon battery and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111631608.0A CN114497452A (en) | 2021-12-28 | 2021-12-28 | Positive electrode material for silicon battery and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114497452A true CN114497452A (en) | 2022-05-13 |
Family
ID=81495914
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111631608.0A Pending CN114497452A (en) | 2021-12-28 | 2021-12-28 | Positive electrode material for silicon battery and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114497452A (en) |
Citations (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005025975A (en) * | 2003-06-30 | 2005-01-27 | Mitsubishi Chemicals Corp | Lithium nickel manganese cobalt based composite oxide for lithium secondary battery positive electrode material, positive electrode for lithium secondary battery using it, and lithium secondary battery |
| KR20050091380A (en) * | 2004-03-12 | 2005-09-15 | 삼성에스디아이 주식회사 | Rechargeable lithium battery |
| JP2005340186A (en) * | 2004-04-27 | 2005-12-08 | Mitsubishi Chemicals Corp | Layered lithium nickel manganese cobalt based composite oxide powder for positive electrode material of lithium secondary battery and manufacturing method thereof, lithium secondary battery positive electrode using it, and lithium secondary battery |
| JP2006172753A (en) * | 2004-12-13 | 2006-06-29 | Mitsubishi Chemicals Corp | Lithium-nickel-manganese-based composite oxide powder for lithium secondary battery positive electrode material, its manufacturing method, positive electrode for lithium secondary battery using it, and lithium secondary battery |
| JP2006269308A (en) * | 2005-03-25 | 2006-10-05 | Mitsubishi Materials Corp | Positive electrode material for nonaqueous secondary battery, its manufacturing method, and nonaqueous secondary battery |
| JP2006331941A (en) * | 2005-05-27 | 2006-12-07 | Sony Corp | Positive electrode active material, positive electrode, and battery |
| JP2008013405A (en) * | 2006-07-06 | 2008-01-24 | Tosoh Corp | Lithium-nickel-manganese-cobalt multiple oxide, method for producing the same, and application of the multiple oxide |
| CN101694876A (en) * | 2009-10-22 | 2010-04-14 | 江西江特锂电池材料有限公司 | Lithium-rich manganese-based anode material and preparation method thereof |
| CN101771145A (en) * | 2010-01-29 | 2010-07-07 | 华中科技大学 | Method for preparing multielement cathode materials for lithium ion batteries |
| CN101944610A (en) * | 2009-07-09 | 2011-01-12 | 河南新飞科隆电源有限公司 | Preparation of stratified lithium ion anode material |
| CN102509784A (en) * | 2011-10-17 | 2012-06-20 | 北大先行科技产业有限公司 | Preparation method of lithium ion battery ternary cathode material |
| CN102983326A (en) * | 2012-09-20 | 2013-03-20 | 横店集团东磁股份有限公司 | Spherical lithium-nickel-cobalt composite oxide positive electrode material preparation method |
| CN103151512A (en) * | 2013-03-13 | 2013-06-12 | 山东海特电子新材料有限公司 | Wet-method preparation process of ternary positive material for lithium ion battery |
| CN103232069A (en) * | 2013-03-20 | 2013-08-07 | 江苏凯力克钴业股份有限公司 | Lithium ion battery lithium-rich manganese base positive electrode material preparation method |
| CN103456946A (en) * | 2013-09-12 | 2013-12-18 | 刘志航 | Anode material for lithium ion battery |
| CN103956477A (en) * | 2014-04-30 | 2014-07-30 | 上海电力学院 | Preparation method of cathode material of lithium-rich ternary compound lithium ion battery |
| CN104779385A (en) * | 2015-04-21 | 2015-07-15 | 哈尔滨工业大学（威海） | High-specific capacity lithium ion battery cathode material and preparation method thereof |
| CN104979549A (en) * | 2015-07-29 | 2015-10-14 | 杭州朗鑫新材料科技有限公司 | Sheet lithium-enriched manganese-based anode material for lithium-ion battery as well as preparation method and application of sheet lithium-enriched manganese-based anode material |
| CN105612124A (en) * | 2013-10-10 | 2016-05-25 | 三井金属矿业株式会社 | Method for manufacturing over-lithiated layered lithium metal composite oxide |
| CN105895906A (en) * | 2016-05-11 | 2016-08-24 | 双登集团股份有限公司 | Lithium-doped ternary lithium-ion battery positive electrode material and preparation method thereof |
| CN106410186A (en) * | 2016-11-17 | 2017-02-15 | 天津理工大学 | Preparation method and application of lithium-rich layered oxide cathode material |
| CN108767239A (en) * | 2018-06-07 | 2018-11-06 | 四川富骅新能源科技有限公司 | A kind of nickelic low cobalt tertiary cathode material and preparation method thereof |
| CN109119612A (en) * | 2018-08-27 | 2019-01-01 | 高点(深圳)科技有限公司 | Positive electrode material precursor and preparation method thereof, positive electrode and preparation method thereof, Anode and battery |
| CN110422890A (en) * | 2019-06-25 | 2019-11-08 | 当升科技(常州)新材料有限公司 | Anode material for lithium-ion batteries and preparation method thereof and lithium ion cell positive and lithium ion battery |
| CN111033832A (en) * | 2018-01-19 | 2020-04-17 | 株式会社Lg化学 | Positive electrode active material for lithium secondary battery, method for producing same, positive electrode for lithium secondary battery comprising same, and lithium secondary battery |
| CN111082041A (en) * | 2019-12-27 | 2020-04-28 | 中国科学院宁波材料技术与工程研究所 | Lithium-rich multi-element positive electrode material, preparation method thereof, positive electrode and lithium ion power battery |
| CN113707874A (en) * | 2021-08-26 | 2021-11-26 | 天津理工大学 | Preparation method of single-crystal high-nickel layered cathode material |
-
2021
- 2021-12-28 CN CN202111631608.0A patent/CN114497452A/en active Pending
Patent Citations (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005025975A (en) * | 2003-06-30 | 2005-01-27 | Mitsubishi Chemicals Corp | Lithium nickel manganese cobalt based composite oxide for lithium secondary battery positive electrode material, positive electrode for lithium secondary battery using it, and lithium secondary battery |
| KR20050091380A (en) * | 2004-03-12 | 2005-09-15 | 삼성에스디아이 주식회사 | Rechargeable lithium battery |
| JP2005340186A (en) * | 2004-04-27 | 2005-12-08 | Mitsubishi Chemicals Corp | Layered lithium nickel manganese cobalt based composite oxide powder for positive electrode material of lithium secondary battery and manufacturing method thereof, lithium secondary battery positive electrode using it, and lithium secondary battery |
| JP2006172753A (en) * | 2004-12-13 | 2006-06-29 | Mitsubishi Chemicals Corp | Lithium-nickel-manganese-based composite oxide powder for lithium secondary battery positive electrode material, its manufacturing method, positive electrode for lithium secondary battery using it, and lithium secondary battery |
| JP2006269308A (en) * | 2005-03-25 | 2006-10-05 | Mitsubishi Materials Corp | Positive electrode material for nonaqueous secondary battery, its manufacturing method, and nonaqueous secondary battery |
| JP2006331941A (en) * | 2005-05-27 | 2006-12-07 | Sony Corp | Positive electrode active material, positive electrode, and battery |
| JP2008013405A (en) * | 2006-07-06 | 2008-01-24 | Tosoh Corp | Lithium-nickel-manganese-cobalt multiple oxide, method for producing the same, and application of the multiple oxide |
| CN101944610A (en) * | 2009-07-09 | 2011-01-12 | 河南新飞科隆电源有限公司 | Preparation of stratified lithium ion anode material |
| CN101694876A (en) * | 2009-10-22 | 2010-04-14 | 江西江特锂电池材料有限公司 | Lithium-rich manganese-based anode material and preparation method thereof |
| CN101771145A (en) * | 2010-01-29 | 2010-07-07 | 华中科技大学 | Method for preparing multielement cathode materials for lithium ion batteries |
| CN102509784A (en) * | 2011-10-17 | 2012-06-20 | 北大先行科技产业有限公司 | Preparation method of lithium ion battery ternary cathode material |
| CN102983326A (en) * | 2012-09-20 | 2013-03-20 | 横店集团东磁股份有限公司 | Spherical lithium-nickel-cobalt composite oxide positive electrode material preparation method |
| CN103151512A (en) * | 2013-03-13 | 2013-06-12 | 山东海特电子新材料有限公司 | Wet-method preparation process of ternary positive material for lithium ion battery |
| CN103232069A (en) * | 2013-03-20 | 2013-08-07 | 江苏凯力克钴业股份有限公司 | Lithium ion battery lithium-rich manganese base positive electrode material preparation method |
| CN103456946A (en) * | 2013-09-12 | 2013-12-18 | 刘志航 | Anode material for lithium ion battery |
| CN105612124A (en) * | 2013-10-10 | 2016-05-25 | 三井金属矿业株式会社 | Method for manufacturing over-lithiated layered lithium metal composite oxide |
| CN103956477A (en) * | 2014-04-30 | 2014-07-30 | 上海电力学院 | Preparation method of cathode material of lithium-rich ternary compound lithium ion battery |
| CN104779385A (en) * | 2015-04-21 | 2015-07-15 | 哈尔滨工业大学（威海） | High-specific capacity lithium ion battery cathode material and preparation method thereof |
| CN104979549A (en) * | 2015-07-29 | 2015-10-14 | 杭州朗鑫新材料科技有限公司 | Sheet lithium-enriched manganese-based anode material for lithium-ion battery as well as preparation method and application of sheet lithium-enriched manganese-based anode material |
| CN105895906A (en) * | 2016-05-11 | 2016-08-24 | 双登集团股份有限公司 | Lithium-doped ternary lithium-ion battery positive electrode material and preparation method thereof |
| CN106410186A (en) * | 2016-11-17 | 2017-02-15 | 天津理工大学 | Preparation method and application of lithium-rich layered oxide cathode material |
| CN111033832A (en) * | 2018-01-19 | 2020-04-17 | 株式会社Lg化学 | Positive electrode active material for lithium secondary battery, method for producing same, positive electrode for lithium secondary battery comprising same, and lithium secondary battery |
| CN108767239A (en) * | 2018-06-07 | 2018-11-06 | 四川富骅新能源科技有限公司 | A kind of nickelic low cobalt tertiary cathode material and preparation method thereof |
| CN109119612A (en) * | 2018-08-27 | 2019-01-01 | 高点(深圳)科技有限公司 | Positive electrode material precursor and preparation method thereof, positive electrode and preparation method thereof, Anode and battery |
| CN110422890A (en) * | 2019-06-25 | 2019-11-08 | 当升科技(常州)新材料有限公司 | Anode material for lithium-ion batteries and preparation method thereof and lithium ion cell positive and lithium ion battery |
| CN111082041A (en) * | 2019-12-27 | 2020-04-28 | 中国科学院宁波材料技术与工程研究所 | Lithium-rich multi-element positive electrode material, preparation method thereof, positive electrode and lithium ion power battery |
| CN113707874A (en) * | 2021-08-26 | 2021-11-26 | 天津理工大学 | Preparation method of single-crystal high-nickel layered cathode material |
Non-Patent Citations (3)
| Title |
|---|
| 叶艳艳;张海朗;: "锂离子电池富锂正极材料Li[Li_(0.2)Ni_(0.16)Mn_(0.56)Co_(0.06)Al_(0.02)]O_2的合成和电化学性能", 化工新型材料, no. 01 * |
| 王先友;白艳松;杨秀康;舒洪波;吴强;: "锂含量对富锂正极材料Li_(1+x)[Ni_(0.5)Co_(0.2)Mn_(0.3)]_(1-x)O_2(x=0.091,0.115,0.138)结构、形貌及电化学性能的影响", 湘潭大学自然科学学报, no. 03 * |
| 赵航;魏闯;康鑫;李素平;: "锂离子电池三元正极材料的研究进展", 中国陶瓷, no. 05 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112750999B (en) | Cathode material, preparation method thereof and lithium ion battery | |
| CN114790013B (en) | Sodium ion battery positive electrode active material capable of self-supplementing sodium, preparation method and application thereof | |
| CN106684323A (en) | Ternary lithium-ion battery cathode material improved by active oxide multiply and preparation method thereof | |
| CN111952590A (en) | Lithium ion battery positive electrode material for improving safety and cycle performance and preparation method thereof | |
| CN109888273B (en) | Preparation method of K, Ti element co-doped high-nickel-base ternary cathode material | |
| CN112047382B (en) | Positive electrode material and preparation method and application thereof | |
| CN111725514A (en) | Modification method of high-nickel ternary cathode material of lithium ion battery | |
| CN113991079A (en) | Composite cathode material and preparation method thereof | |
| CN113363497A (en) | Ternary material, preparation method and battery | |
| CN111180724A (en) | Preparation method of ternary single crystal cathode material | |
| CN106910887A (en) | A kind of lithium-rich manganese-based anode material, its preparation method and the lithium ion battery comprising the positive electrode | |
| CN111740098A (en) | High-nickel cathode material with surface layer doped with Mn and rock salt phase thin layer and preparation method thereof | |
| CN110137464B (en) | Lithium-rich nickel cobalt manganese oxide positive electrode material coated by vanadium lithium molybdate, positive electrode piece and preparation method thereof, and lithium battery | |
| CN109509875B (en) | High-rate single crystal lithium nickel cobalt manganese oxide cathode material and preparation method thereof | |
| CN116995224A (en) | Layered low-cobalt nickel-rich positive electrode material and preparation method thereof | |
| CN115231629A (en) | Preparation method of lithium-passing layered manganese-based oxide coated ternary cathode material | |
| CN114804235A (en) | High-voltage nickel cobalt lithium manganate positive electrode material and preparation method and application thereof | |
| CN116314731B (en) | Sodium ion battery anode material, precursor thereof, preparation method and application | |
| CN116314759A (en) | High-nickel positive electrode material, preparation method thereof and lithium ion battery | |
| KR101762282B1 (en) | High capacity cathode material improved thermal stability for lithium ion battery and a method of manufacturing the same | |
| CN114497452A (en) | Positive electrode material for silicon battery and preparation method and application thereof | |
| CN112736240B (en) | High-residual-alkali lithium ion multi-element positive electrode material and preparation method thereof | |
| CN116230882A (en) | High-nickel ternary positive electrode material for lithium battery, preparation method and lithium battery | |
| CN115286042A (en) | Lithium-rich manganese-based positive electrode material of lithium ion battery and preparation method thereof | |
| CN114927777A (en) | Ultrahigh lithium content material and self-supplementing lithium composite positive electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |