CN112747590A - Dynamic synthesis device and dynamic synthesis method for ternary materials of lithium ion battery - Google Patents
Dynamic synthesis device and dynamic synthesis method for ternary materials of lithium ion battery Download PDFInfo
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- CN112747590A CN112747590A CN201911047010.XA CN201911047010A CN112747590A CN 112747590 A CN112747590 A CN 112747590A CN 201911047010 A CN201911047010 A CN 201911047010A CN 112747590 A CN112747590 A CN 112747590A
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B7/00—Rotary-drum furnaces, i.e. horizontal or slightly inclined
- F27B7/14—Rotary-drum furnaces, i.e. horizontal or slightly inclined with means for agitating or moving the charge
- F27B7/16—Rotary-drum furnaces, i.e. horizontal or slightly inclined with means for agitating or moving the charge the means being fixed relatively to the drum, e.g. composite means
- F27B7/161—Rotary-drum furnaces, i.e. horizontal or slightly inclined with means for agitating or moving the charge the means being fixed relatively to the drum, e.g. composite means the means comprising projections jutting out from the wall
- F27B7/162—Rotary-drum furnaces, i.e. horizontal or slightly inclined with means for agitating or moving the charge the means being fixed relatively to the drum, e.g. composite means the means comprising projections jutting out from the wall the projections consisting of separate lifting elements, e.g. lifting shovels
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B7/00—Rotary-drum furnaces, i.e. horizontal or slightly inclined
- F27B7/14—Rotary-drum furnaces, i.e. horizontal or slightly inclined with means for agitating or moving the charge
- F27B7/16—Rotary-drum furnaces, i.e. horizontal or slightly inclined with means for agitating or moving the charge the means being fixed relatively to the drum, e.g. composite means
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B7/00—Rotary-drum furnaces, i.e. horizontal or slightly inclined
- F27B7/20—Details, accessories, or equipment peculiar to rotary-drum furnaces
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- 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
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- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- 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
- H01M4/48—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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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B7/00—Rotary-drum furnaces, i.e. horizontal or slightly inclined
- F27B7/14—Rotary-drum furnaces, i.e. horizontal or slightly inclined with means for agitating or moving the charge
- F27B7/16—Rotary-drum furnaces, i.e. horizontal or slightly inclined with means for agitating or moving the charge the means being fixed relatively to the drum, e.g. composite means
- F27B7/161—Rotary-drum furnaces, i.e. horizontal or slightly inclined with means for agitating or moving the charge the means being fixed relatively to the drum, e.g. composite means the means comprising projections jutting out from the wall
- F27B7/162—Rotary-drum furnaces, i.e. horizontal or slightly inclined with means for agitating or moving the charge the means being fixed relatively to the drum, e.g. composite means the means comprising projections jutting out from the wall the projections consisting of separate lifting elements, e.g. lifting shovels
- F27B2007/163—Rotary-drum furnaces, i.e. horizontal or slightly inclined with means for agitating or moving the charge the means being fixed relatively to the drum, e.g. composite means the means comprising projections jutting out from the wall the projections consisting of separate lifting elements, e.g. lifting shovels using only a ring of lifting elements to lift the charge
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27M—INDEXING SCHEME RELATING TO ASPECTS OF THE CHARGES OR FURNACES, KILNS, OVENS OR RETORTS
- F27M2003/00—Type of treatment of the charge
- F27M2003/04—Sintering
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the field of lithium ion batteries, and discloses a dynamic synthesis device and a dynamic synthesis method for ternary materials of lithium ion batteries. The device comprises: the device comprises a conical feeding unit (1), wherein a first opening (2) is formed in the conical top end of the conical feeding unit (1); a furnace tube (5); the converter body (3), the converter body (3) is nested outside the furnace tube (5); the material raising plate (4), one side of the material raising plate (4) is connected with the inner wall of the furnace tube (5); a broken mace (7), the broken mace (7) being disposed along the axis of the furnace tube (5). The device and the synergistic process provided by the invention are improved, and the defects of nonuniform lithium distribution among material particles, high energy consumption, low production efficiency and the like in the sintering of the ternary material of the lithium ion battery are overcome.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a dynamic synthesis device and a dynamic synthesis method for ternary materials of a lithium ion battery.
Background
The lithium nickel cobalt manganese (or aluminum) ternary material has been widely applied to the fields of small lithium ion batteries for consumer electronics such as mobile phones and notebook computers, and large power batteries for electric bicycles and electric automobiles due to the advantages of high energy density, good cycle performance, low self-discharge rate and the like.
The performance of the ternary material plays a decisive role in the performance of the lithium ion battery, and the physicochemical performance and the electrochemical performance of the ternary material are not only related to the proportion of three elements of Ni-Co-Mn (or Al), but also closely related to the preparation process of the ternary material.
Currently, the industrialized ternary material is mainly prepared by taking a hydroxide precursor of nickel-cobalt-manganese (or aluminum) and lithium carbonate or lithium hydroxide monohydrate as raw materials, calcining the raw materials in a roller kiln or a pushed slab kiln, and loading the raw materials in a sagger in a static state by static sintering.
The method for synthesizing the ternary material has simple process and is suitable for large-scale production, but has obvious defects:
(1) lithium among material particles is unevenly distributed
When the Ni content is less than 0.5, lithium carbonate is generally used as a lithium source, and a hydroxide of nickel, cobalt and manganese (or aluminum) is used as a precursor for synthesis. The loss on ignition during calcination is 25-27%, of which about 14% is discharged in the form of water. When the Ni content is more than 0.6, lithium hydroxide monohydrate is generally adopted as a lithium source, and hydroxide of nickel, cobalt and manganese (or aluminum) is adopted as a precursor for synthesis. The loss on ignition during calcination is 29-31%, and the lost material is mainly discharged in the form of water. In the roasting process, lithium moves upwards from the bottom of the saggar along with the evaporation of water, so that the lithium content of the bottom material is low, the lithium content of the upper material is high, and the lithium distribution among material particles is uneven.
(2) Low heat efficiency and high energy consumption
When the traditional roller kiln or pushed slab kiln is used for calcining, the material heating mode is radiation heating, the heat transfer efficiency is low, and therefore, longer roasting time is needed; in addition, the saggar can absorb partial heat during roasting, and heat loss is caused due to heat dissipation of two ends of the kiln due to poor sealing performance. Therefore, the traditional roller kiln or pushed slab kiln has low thermal efficiency and high energy consumption.
(3) The sagger has large consumption, increases the production cost and pollutes the environment
The sagger can be damaged in the repeated heating and cooling process and needs to be replaced frequently, so that the production cost is increased, a lot of solid wastes are generated, and the environment is polluted.
(4) High oxygen consumption and low production efficiency
When the ternary material is prepared, oxygen is needed to participate to complete the sintering reaction. When utilizing traditional roller kilns or pushed slab kiln to sinter the material, the material on sagger top layer can fully contact with oxygen, but the oxygen that the bottom material contacted is just more limited, consequently has great restriction to the sagger thickness of feeding, and the charge is less, and production efficiency is low.
In order to overcome the problems, CN1710735A adopts a rotary furnace to carry out roasting synthesis on the anode material, although the use amount of saggars is saved by the technology, the roasting time is still 20-40 hours, the difference from the traditional static roasting process is smaller, and the production efficiency is still lower; in addition, the furnace tube is not internally provided with a material raising plate, and the rotating speed is only 2-5r/min, so the secondary mixing effect of the materials is poor. In addition, CN208567497U has improved the internal structure of the converter tube, has added the spiral stock guide, and the pottery inlayer is formed integrally with spiral stock guide, but this equipment still has following shortcoming: (1) the structure has complex manufacturing process, poor thermal shock resistance and short service life, and can hardly be maintained if damaged; (2) the gas flow direction is consistent with the material flow direction, so that a large amount of water which is removed when the ternary material is sintered can be condensed at the discharge end, the water content of the finished material is increased, and the performance of the material is reduced.
Disclosure of Invention
The invention aims to provide a dynamic sintering process and a dynamic sintering device for a ternary material of a lithium ion battery, which overcome the defects of uneven lithium distribution among material particles, high energy consumption caused by overlong roasting time, large sagger consumption, high oxygen consumption, low production efficiency and the like in the sintering of the ternary material of the lithium ion battery through the improvement of a roasting device or a synergistic process.
In order to achieve the above object, a first aspect of the present invention provides a lithium ion battery ternary material dynamic synthesis device, comprising:
the device comprises a conical feeding unit, a first feeding unit and a second feeding unit, wherein a first opening is formed in the conical top end of the conical feeding unit;
one end of the furnace tube is connected with the conical bottom end of the conical feeding unit, and the other end of the furnace tube is provided with a second opening;
the converter body is nested outside the furnace tube, and an included angle of more than 0 degree is formed between the converter body and the central shaft of the furnace tube, so that the central shaft of the furnace tube is inclined upwards relative to the central shaft of the converter body;
one side of the lifting plate is connected with the inner wall of the furnace tube;
a broken mace disposed along an axis of the furnace tube.
The second aspect of the invention provides a dynamic synthesis method of a ternary material of a lithium ion battery, which comprises the following steps:
(1) general formula Ni1-x-yCoxMy(OH)2The precursor material, lithium source and additive are mixed to obtain a first mixture, M is Mn or Al，0<x<0.5，0<y<0.5；
(2) Continuously introducing the first mixture into the device of the first aspect for roasting to obtain a roasted material I;
(3) crushing the roasted material I to obtain the ternary material of the lithium ion battery,
wherein, in step (2), the calcination is carried out in the presence of an oxygen-containing gas, and the first mixture is countercurrently contacted with the oxygen-containing gas in a furnace tube.
Compared with the prior art, the invention has the following advantages:
(1) by designing the material raising plates in the furnace tubes of the converter equipment, the secondary mixing strength of the materials is enhanced, and the mass transfer speed among different materials is improved, so that the lithium distribution uniformity among material particles is improved;
(2) the shape of the furnace tube is designed to be a single cone, the furnace tube has a certain horizontal inclination angle, and the rotating speed of the furnace tube is increased, so that the heat transfer speed of materials is increased, the roasting time of the materials is shortened, the production efficiency is improved, and the energy consumption is reduced;
(3) through the improvement of the roasting device and the synergistic synthesis method, the defects of uneven lithium distribution among material particles, high energy consumption, large sagger consumption, high oxygen consumption, low production efficiency and the like in the sintering of the ternary material of the lithium ion battery are overcome.
Additional features and advantages of the invention will be described in detail in the detailed description which follows.
Drawings
FIG. 1 is a front view of a lithium ion battery ternary material dynamic synthesis device provided by the invention;
FIG. 2 is a right side view of a lithium ion battery ternary material dynamic synthesis device provided by the invention;
FIG. 3 is a scanning electron micrograph of the ternary material prepared in example 1;
FIG. 4 is a graph of the cycling performance of the ternary material prepared in example 1.
Description of the reference numerals
1. Conical feeding unit 2, first opening 3 and converter body
4. The material raising plate 5, the furnace tube 6 and the second opening
7. Broken wolf tooth stick 8, furnace tube outer wall 9, corundum ceramic plate
10. Ceramic bolt
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides a lithium ion battery ternary material dynamic synthesis device, which comprises:
the device comprises a conical feeding unit, a first feeding unit and a second feeding unit, wherein a first opening is formed in the conical top end of the conical feeding unit;
one end of the furnace tube is connected with the conical bottom end of the conical feeding unit, and the other end of the furnace tube is provided with a second opening;
the converter body is nested outside the furnace tube, and an included angle of more than 0 degree is formed between the converter body and the central shaft of the furnace tube, so that the central shaft of the furnace tube is inclined upwards relative to the central shaft of the converter body;
one side of the lifting plate is connected with the inner wall of the furnace tube;
a broken mace disposed along an axis of the furnace tube.
In the invention, the cone top refers to the surface of the conical object with smaller area, and correspondingly, the cone bottom refers to the surface of the conical object with larger area.
In the invention, the furnace tube is preferably of a double-layer structure, and the furnace wall (particularly the outer wall) of the furnace tube is preferably made of high-temperature-resistant steel with the model number of 1Cr24Ni20Si 2.
Preferably, a corundum ceramic lining is arranged on the inner wall of the furnace tube.
Preferably, the corundum ceramic lining is formed by connecting corundum ceramic plates with radian, the number of the corundum ceramic plates is more than or equal to 2. And the corundum ceramic plates with radians are connected to form the inner wall of the furnace tube.
Preferably, each corundum ceramic plate has a length of 100-1000mm, a width of 50-150mm and a thickness of 2-10 mm. The sizes of the corundum ceramic plates of the present invention may be the same or different, and the present invention is not particularly limited thereto as long as the corundum ceramic plates can form the inner wall of the furnace tube of the present invention.
Preferably, each of the corundum ceramic plates is fixed to the wall of the furnace tube by a ceramic bolt.
Preferably, the width of the material raising plate is 10-30% of the inner diameter of the furnace tube.
Preferably, the length of each broken mace is 30-65% of the inner diameter of the furnace tube. The present invention has no particular limitation on the angles between the plurality of mace rods arranged around the axis, the number of mace rods on the same circumference, the corresponding distances between different circumferences, etc., and those skilled in the art can specifically select the method according to the present invention and the actual conditions such as the degree of crushing to be obtained.
Preferably, the two ends of the furnace tube are provided with sealing flanges, for example, the sealing flange at one end of the furnace tube is connected with the conical feeding unit.
Preferably, a magnetic fluid rotating piece is arranged on the sealing flange.
Preferably, the included angle between the converter body and the central axis of the furnace tube is 1-5 °.
A preferred embodiment of the lithium ion battery ternary material dynamic synthesis device of the present invention is provided below with reference to fig. 1 and 2.
The device comprises:
the feeding device comprises a conical feeding unit 1, wherein a first opening 2 is formed in the conical top end of the conical feeding unit 1;
one end of the furnace tube 5 is connected with the conical bottom end of the conical feeding unit 1, and the other end of the furnace tube 5 is provided with a second opening 6;
the converter body 3 is nested outside the furnace tube 5, and an included angle of more than 0 degree is formed between the converter body 3 and the central shaft of the furnace tube 5, so that the central shaft of the furnace tube 5 inclines upwards relative to the central shaft of the converter body 3;
the material raising plate 4, one side of the material raising plate 4 is connected with the inner wall of the furnace tube 5;
a broken mace 7, the broken mace 7 is arranged along the axis of the furnace tube 5.
In the present invention, the furnace tube 5 preferably has a double-layer structure.
Preferably, the furnace tube outer wall 8 of the furnace tube 5 is high temperature resistant steel with the model number of 1Cr24Ni20Si 2.
Preferably, a corundum ceramic lining is arranged on the inner wall of the furnace tube 5.
Preferably, the corundum ceramic lining is formed by connecting corundum ceramic plates 9 with radian, the number of the corundum ceramic plates is more than or equal to 2.
Preferably, each of the corundum ceramic plates 9 is fixed to the inner wall of the furnace tube 5 by a ceramic bolt 10.
Preferably, the inside of the furnace tube of the device is formed by connecting corundum ceramic plates, so that the alkali corrosion resistance of the furnace tube is enhanced, the thermal shock impact of the heating or cooling process on the ceramic lining is reduced, the service life of the furnace tube is prolonged, and meanwhile, the paving of the corundum ceramic plates ensures that materials are not directly contacted with the high-temperature resistant steel on the outer layer of the furnace tube, so that the content of magnetic impurities of the materials can be reduced.
Preferably, the width of the material raising plate 4 is 10-30% of the inner diameter of the furnace tube 5.
Preferably, the length of each broken mace 7 is 30-65% of the inner diameter of the furnace tube 5.
Preferably, sealing flanges are arranged at two ends of the furnace tube 5.
Preferably, the included angle between the central axis of the converter body 3 and the central axis of the furnace tube 5 is 1 to 5 °.
As described above, the second aspect of the present invention provides a method for dynamically synthesizing a ternary material for a lithium ion battery, the method comprising:
(1) general formula Ni1-x-yCoxMy(OH)2Mixing the precursor material, lithium source and additive to obtain a first mixture, wherein M is Mn or Al, and 0<x<0.5，0<y<0.5；
(2) Continuously introducing the first mixture into the device of the first aspect for roasting to obtain a roasted material I;
(3) crushing the roasted material I to obtain the ternary material of the lithium ion battery,
wherein, in step (2), the calcination is carried out in the presence of an oxygen-containing gas, and the first mixture is countercurrently contacted with the oxygen-containing gas in a furnace tube.
In the present invention, the continuous introduction means that the mixture is introduced into the apparatus at a constant rate per unit time, and may be introduced uniformly at the same mass per unit time or introduced non-uniformly at different masses per unit time.
Preferably, in the step (2), the roasting conditions include: the temperature is 700 ℃ and 1000 ℃, and the average residence time of the first mixture in the furnace tube is 5-10 h.
Preferably, the rotating speed of the furnace tube in the device is 6-10 rpm.
Preferably, in the step (2), the flow rate of the oxygen-containing gas in the calcination is 1 to 3m3/h。
Preferably, in step (1), the precursor substance, the lithium source, and the additive are used in amounts such that the molar ratio of lithium element to a metal element other than lithium element in the first mixture is 1.02 to 1.1: 1. that is, Ni is a hydroxide precursor of Ni, Co, Mn (or Al)1-x-yCoxMy(OH)2(M ═ Mn or Al, 0)<x<0.5，0<y<0.5), lithium source (Li)2CO3Or LiOH. H2One or two of O) and additives in terms of moles of lithium/metal other than lithiumThe ratio is 1.02-1.1:1, mixing the ingredients.
Preferably, the additive is selected from hydroxides containing at least one element of Mg, Al, Ti, Zr, Nb, Y and La, oxides containing at least one element of Mg, Al, Ti, Zr, Nb, Y and La, and salts containing at least one element of Mg, Al, Ti, Zr, Nb, Y and La.
The following provides a preferred embodiment of the lithium ion battery ternary material dynamic synthesis method of the present invention in conjunction with the apparatus shown in fig. 1 and 2:
(1) general formula Ni1-x-yCoxMy(OH)2Mixing the precursor material, lithium source and additive to obtain a first mixture, wherein M is Mn or Al, and 0<x<0.5，0<y<0.5；
(2) The first mixture is continuously introduced into a conical feeding unit 1 in the device from a first opening 2, the first mixture enters a furnace tube 5 from the conical feeding unit 1 for roasting, and is pre-crushed by a crushing wolf tooth rod 7 contained in the first mixture, and a material raising plate 4 connected with the inner wall of the furnace tube 5 can strengthen the secondary mixing strength of materials and improve the mass transfer speed among different materials, so that the lithium distribution uniformity among material particles is improved; the resulting calcined material I is drawn out through a second opening 6 of the apparatus; at the same time, the oxygen-containing gas participating in the calcination is continuously introduced from the second opening 6 and is continuously extracted from the first opening 2;
(3) and crushing the roasted material I to obtain the ternary material of the lithium ion battery.
In addition, in order to conveniently introduce and draw the material from the device, a device for facilitating the material to enter and exit, such as a funnel, may be provided at the material inlet and the material outlet of the device, and the present invention is not particularly limited thereto.
The present invention will be described in detail below by way of examples.
In the following examples, all the raw materials are commercially available products unless otherwise specified.
Wherein the charge-discharge voltage range is 2.75-4.3V, the charge-discharge multiplying power is 0.2C, and the cycle number is 100.
Example 1
Mixing Ni0.8Co0.1Mn0.1(OH)2、LiOH·H2O and Al (OH)3Weighing the components according to the molar ratio of Li (Ni + Co + Mn + Al) to 1.02, wherein Ni is0.8Co0.1Mn0.1(OH)250kg of the raw materials are uniformly mixed in a high-efficiency mixer, and the mixed materials are continuously introduced into a conical feeding unit in the device from a first opening and then enter a furnace tube for roasting. Wherein the set temperature of the converter is 740 ℃, the rotating speed is 6rpm, the horizontal inclination angle of the furnace tube is 1 degree, and the oxygen flow is 2m3The average residence time of the solid mixture in the furnace is 10 h. Discharging the roasted material from the second opening, further crushing and sieving to obtain Li [ (Ni)0.8Co0.1Mn0.1)0.99Al0.01O2(NCM811-Al) ternary material.
Example 2
Mixing Ni0.8Co0.1Mn0.1(OH)2、LiOH·H2O and additive Mg (OH)2Weighing the components according to the molar ratio of Li (Ni + Co + Mn + Mg) to 1.1, wherein Ni is0.8Co0.1Mn0.1(OH)250kg of the raw materials are uniformly mixed in a high-efficiency mixer, and the mixed materials are continuously introduced into a conical feeding unit in the device from a first opening and then enter a furnace tube for roasting. Wherein the set temperature of the converter is 750 ℃, the rotating speed is 6rpm, the horizontal inclination angle of the furnace tube is 3 degrees, and the oxygen flow is 2m3The average residence time of the solid mixture in the furnace is 5 h. Discharging the roasted material from the second opening, further crushing and sieving to obtain Li [ (Ni)0.8Co0.1Mn0.1)0.995Mg0.005]O2(NCM811-Mg) ternary material.
Example 3
Mixing Ni0.5Co0.2Mn0.3(OH)2、LiOH·H2O and Nb2O5According to the mol ratio of Li (Ni + Co + Mn + Nb) to 1.05 in proportion of Ni0.5Co0.2Mn0.3(OH)250kg of the raw materials are uniformly mixed in a high-efficiency mixer, and the mixed materials are continuously introduced into a conical feeding unit in the device from a first opening and then enter a furnace tube for roasting. Wherein the set temperature of the converter is 950 ℃, the rotating speed is 10rpm, the horizontal inclination angle of the furnace tube is 1 degree, and the oxygen flow is 1m3The average residence time of the solid mixture in the furnace is 8 h. Discharging the roasted material from the second opening, further crushing and sieving to obtain Li [ (Ni)0.5Co0.2Mn0.3)0.992Nb0.008]O2(NCM523-Nb) ternary material.
Example 4
Mixing Ni1/3Co1/3Mn1/3(OH)2、LiOH·H2O、Mg(OH)2、TiO2And Al (OH)3Weighing the components according to the molar ratio of Li (Ni + Co + Mn + Mg + Ti + Al) to 1.05, wherein Ni is1/3Co1/3Mn1/3(OH)250kg of the raw materials are uniformly mixed in a high-efficiency mixer, and the mixed materials are continuously introduced into a conical feeding unit in the device from a first opening and then enter a furnace tube for roasting. Wherein the set temperature of the converter is 1000 ℃, the rotating speed is 6rpm, the horizontal inclination angle of the furnace tube is 1 degree, and the oxygen flow is 1m3The average residence time of the solid material in the furnace is 10 h. Discharging the roasted material from the second opening, further crushing and sieving to obtain doped Li [ (Ni)1/3Co1/3Mn1/3)0.98Mg0.005Al0.01Ti0.005]O2(NCM111-MAT) ternary material.
Example 5
Mixing Ni0.9Co0.05Mn0.05(OH)2、LiOH·H2O and Y2O3Weighing the mixture according to the molar ratio of Li (Ni + Co + Mn + Y) to 1.05, wherein Ni is0.9Co0.05Mn0.05(OH)250kg, mixed homogeneously in a high-efficiency mixer, the mixture being introduced continuously from a first opening into a cone in the apparatusAnd in the material unit, further entering a furnace tube for roasting. Wherein the set temperature of the converter is 700 ℃, the rotating speed is 8rpm, the horizontal inclination angle of the furnace tube is 2 degrees, and the oxygen flow is 3m3The average residence time of the solid mixture in the furnace is 8 h. Discharging the roasted material from the second opening, further crushing and sieving to obtain Li [ (Ni)0.9Co0.05Mn0.05)0.99Y0.01]O2(NCM955-Y) ternary material.
Test example
The ternary materials prepared in the above examples were tested for SEM surface topography and cycle performance, respectively.
The invention illustratively provides LiNi prepared in example 10.8Co0.1Mn0.1O2As shown in FIG. 3, the SEM image of the (NCM811) ternary material can be seen from FIG. 3, the material is spherical particles with regular morphology, the particle size is about 10 μm, the secondary particles are composed of primary particles with the particle size of 300-500 nm, and the crystallization performance is good.
In addition, the present invention illustratively provides Li [ (Ni) prepared in example 10.8Co0.1Mn0.1)0.99Al0.01O2As shown in FIG. 4, the cycle performance curve of the (NCM811-Al) ternary material can be seen from FIG. 4 that the material has good electrochemical performance, the first discharge specific capacity is 201.1mAh/g, and the cycle capacity retention rate is 93.2% after 100 times.
Also, the cycle performance curves of the ternary materials provided by the remaining examples of the present invention are similar to those of FIG. 4. That is, the present invention can obtain a material having excellent properties by using a shorter firing time.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (13)
1. A lithium ion battery ternary material dynamic synthesis device is characterized in that the device comprises:
the device comprises a conical feeding unit (1), wherein a first opening (2) is formed in the conical top end of the conical feeding unit (1);
one end of the furnace tube (5) is connected with the conical bottom end of the conical feeding unit (1), and the other end of the furnace tube (5) is provided with a second opening (6);
the converter body (3) is nested outside the furnace tube (5), and an included angle of more than 0 degree is formed between the converter body (3) and the central axis of the furnace tube (5), so that the central axis of the furnace tube (5) inclines upwards relative to the central axis of the converter body (3);
the material raising plate (4), one side of the material raising plate (4) is connected with the inner wall of the furnace tube (5);
a broken mace (7), the broken mace (7) being disposed along the axis of the furnace tube (5).
2. The device according to claim 1, characterized in that a corundum ceramic lining is arranged on the inner wall of the furnace tube (5);
preferably, the corundum ceramic lining is formed by connecting corundum ceramic plates with radian, the number of the corundum ceramic plates is more than or equal to 2;
preferably, each corundum ceramic plate has a length of 100-1000mm, a width of 50-150mm and a thickness of 2-10 mm.
3. The device according to claim 2, characterized in that each of said corundum-ceramic plates is fixed to the wall of said furnace tube (5) by means of ceramic bolts.
4. A device according to any one of claims 1-3, characterized in that the width of the lifter plate (4) is 10-30% of the inner diameter of the furnace tube (5).
5. The device according to any one of claims 1 to 4, characterized in that the length of each broken wolf tooth bar (7) is 30-65% of the inner diameter of the furnace tube (5).
6. The device according to any one of claims 1 to 5, characterized in that the furnace tube (5) is provided with sealing flanges at both ends;
preferably, the sealing flange is provided with a magnetic fluid rotating piece.
7. An arrangement according to any one of claims 1-6, characterized in that the angle between the converter body (3) and the central axis of the furnace tube (5) is 1-5 °.
8. A dynamic synthesis method of a ternary material of a lithium ion battery is characterized by comprising the following steps:
(1) general formula Ni1-x-yCoxMy(OH)2Mixing the precursor material, lithium source and additive to obtain a first mixture, wherein M is Mn or Al, and 0<x<0.5，0<y<0.5；
(2) Continuously introducing the first mixture into the device of any one of claims 1-7 for roasting to obtain a roasted material I;
(3) crushing the roasted material I to obtain the ternary material of the lithium ion battery,
wherein, in step (2), the calcination is carried out in the presence of an oxygen-containing gas, and the first mixture is countercurrently contacted with the oxygen-containing gas in a furnace tube.
9. The method of claim 8, wherein in step (2), the roasting conditions comprise: the temperature is 700 ℃ and 1000 ℃, and the average residence time of the first mixture in the furnace tube is 5-10 h.
10. The method according to claim 8 or 9, wherein the furnace tube in the apparatus is rotated at a speed of 6-10 rpm.
11. According to claims 8 to 10The method according to any one of the above items, wherein the flow rate of the oxygen-containing gas during the calcination is 1 to 3m3/h。
12. The method according to any one of claims 8 to 11, wherein in step (1), the precursor substance, the lithium source, and the additive are used in amounts such that a molar ratio of lithium element to a metal element other than lithium element in the first mixture is 1.02 to 1.1: 1.
13. The method according to any of claims 8-12, characterized in that the additive is selected from the group consisting of hydroxides containing at least one element of Mg, Al, Ti, Zr, Nb, Y and La, oxides containing at least one element of Mg, Al, Ti, Zr, Nb, Y and La, and salts containing at least one element of Mg, Al, Ti, Zr, Nb, Y and La.
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| CN201697448U (en) * | 2010-04-23 | 2011-01-05 | 江苏凯力克钴业股份有限公司 | Rotary kiln |
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