CN109686971A - A kind of production method and production rotary kiln of nickelic polynary positive pole material - Google Patents
A kind of production method and production rotary kiln of nickelic polynary positive pole material Download PDFInfo
- Publication number
- CN109686971A CN109686971A CN201811515764.9A CN201811515764A CN109686971A CN 109686971 A CN109686971 A CN 109686971A CN 201811515764 A CN201811515764 A CN 201811515764A CN 109686971 A CN109686971 A CN 109686971A
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- Prior art keywords
- rotary kiln
- kiln
- positive pole
- inclination angle
- pole material
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- 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.)
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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
-
- 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
- F27B7/02—Rotary-drum furnaces, i.e. horizontal or slightly inclined of multiple-chamber or multiple-drum type
-
- 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
- F27B7/08—Rotary-drum furnaces, i.e. horizontal or slightly inclined externally heated
-
- 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
- F27B7/34—Arrangements of heating devices
-
- 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
- F27B7/02—Rotary-drum furnaces, i.e. horizontal or slightly inclined of multiple-chamber or multiple-drum type
- F27B2007/027—Rotary-drum furnaces, i.e. horizontal or slightly inclined of multiple-chamber or multiple-drum type with more than one drum
-
- 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
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a kind of production methods of nickelic polynary positive pole material, link by the way of rotary kiln sintered using two sections, complete the firing process of nickelic polynary positive pole material, replace the mode of traditional roller kilns and saggar carrying sintering.The rotary kiln inner cavity uses the high alumina ceramic material of resistance to oxidation under high temperature, and two sections of rotary kilns can freely adjust inclination angle;At inclination angle when level, material to be burnt heats reaction in rotary kiln;When inclination angle is adjusted to 5 degree or more, rotary kiln carries out discharging.Bearing mode when being sintered is optimized for dynamical fashion by saggar carrying by the present invention, solves the problems, such as that material contacts deficiency with sintering atmosphere during the sintering process.Meanwhile by the process for calcining of two sections of coordinated types, solve the problems, such as that material generates influence of the moisture to process during the sintering process;Simultaneously as dynamic material and sintering atmosphere contact surface increase, reduce sintered gas consumption, energy consumption reduces.
Description
Technical field
The present invention relates to a kind of production methods of nickelic polynary positive pole material.
Background technique
Lithium ion battery (lithium secondary battery) with the advantages of its lightweight, long-life, clean and environmental protection increasingly by battery
The favor of industry.The positive electrode of lithium ion battery is the emphasis of research and development in the industry all the time as its critical material.
Currently, the positive electrode mainstream of lithium ion battery has cobalt acid lithium, LiFePO4, LiMn2O4 and nickel-cobalt-manganese ternary material, and have
The emerging materials such as NCA (nickel cobalt aluminium) system, LOL (rich lithium manganese solid solution) are added thereto, and have obtained extensive commercial applications.Its
In, cobalt nickel lithium manganate ternary material, especially NCA material the characteristics of with its high capacity, high-energy density, are met increasingly
The requirement of high energy density, is more favored.In industry generally by the higher NCA of nickel content the materials such as NCM811 claim
For nickelic multicomponent material.
The method of the positive electrode of existing industrial production high nickel content is usually high temperature solid-state method.Use high nickel content
Hydroxide (i.e. presoma) and lithium hydroxide be raw material, produced in kiln with the method for high temperature sintering after mixing,
Sintering reaction process is broadly divided into two sections, and leading portion is at 600 DEG C hereinafter, participating in the moisture content in the predecessor or raw material of reaction, no
The volatilization and thermal decomposition of stable state substance, back segment are at 600 DEG C or more, and reaction generates nickelic multicomponent material, which generally needs
It wants oxygen to participate in reaction, belongs to oxygen-absorbing reaction.The kiln for using high temperature solid-state method to be burnt into generally promotes air stream in a manner of air blast
It is logical, oxygen required for being burnt into supplying material.But the ratio of oxygen is limited in air, and by largely divulging information, it is that will cause
The heat loss of kiln increases, and the temperature of sintering cannot be guaranteed.And it will cause equipment portions for logical oxygen into the kiln of high temperature
Part oxidation and loss.Material usually to be burnt, which is contained in fire resistant sagger, to be sintered, to enable in saggar material be filled with oxygen
Tap contacts, it is uniform to reach reaction, it is necessary to largely lead to oxygen.
Traditional method uses certain stacking method since material to be burnt is fixed.Such method can only pass through increasing
Oxygen-supply quantity and increasing soaking time section keeps sintering reaction more complete, this has resulted in a large amount of waste of oxygen, causes a large amount of
Idle heat loss;Or the method being burnt into twice is simply taken, it does so and even more extends the production cycle, product but will be caused
It is unstable.The consumption of the energy is not only increased, the material after also inevitably making firing is affected, and grain growth is endless
Entirely, lattice stability is poor, and material homogeneity is bad, and lot stability and chemical property are severely impacted.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the defect of the prior art, a kind of nickelic polynary positive pole material is provided
Production method.
In order to solve the above-mentioned technical problems, the present invention provides the following technical solutions:
One aspect of the invention provides a kind of production method of nickelic polynary positive pole material, use two sections it is rotary kiln sintered
Mode link, complete the firing process of nickelic polynary positive pole material, replace the mode of traditional roller kilns and saggar carrying sintering.
Further, the rotary kiln inner cavity uses the high alumina ceramic material of resistance to oxidation under high temperature, and two sections of rotary kilns
It can freely adjust inclination angle;At inclination angle when level, material to be burnt heats reaction in rotary kiln;When inclination angle is adjusted to 5 degree or more,
Rotary kiln carries out discharging.
Further, leading portion kiln heating temperature range is 500~600 degrees Celsius, is passed through nitrogen from kiln tail in reaction process,
Air draft is forced from kiln hood, control kiln inner pressure is tiny structure;Back segment heating temperature range is 680 degree -780 and spends, in reaction process
It is passed through oxygen from kiln tail, from kiln hood natural exhaust, kiln inner pressure is micro-positive pressure.
Another aspect of the invention provides a kind of nickelic polynary positive pole material production rotary kiln comprising heating mantle, institute
It states and is provided with rotary kiln inner tube in heating mantle, one end of the rotary kiln inner tube is provided with feed inlet, the rotary kiln inner tube
The other end is provided with discharge port;The bottom of the heating mantle is provided with mounting seat close to one end of feed inlet, close to discharge port
One end be provided with lifting inclination angle adjustor.
The beneficial effects obtained by the present invention are as follows being:
Bearing mode when being sintered is optimized for dynamical fashion by saggar carrying by the present invention, solves material in sintering process
In insufficient problem is contacted with sintering atmosphere.Meanwhile by the process for calcining of two sections of coordinated types, material is solved during the sintering process
Lead to the problem of influence of the moisture to process;Simultaneously as dynamic material and sintering atmosphere contact surface increase, make sintered to use gas
Amount is reduced, and energy consumption reduces.The nickelic polynary positive pole material produced by this method, cycle performance are obviously improved, thermal stability
It improves a lot with batch consistency.
Detailed description of the invention
Attached drawing is used to provide further understanding of the present invention, and constitutes part of specification, with reality of the invention
It applies example to be used to explain the present invention together, not be construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the structural schematic diagram of rotary kiln of the present invention.
Specific embodiment
Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings, it should be understood that preferred reality described herein
Apply example only for the purpose of illustrating and explaining the present invention and is not intended to limit the present invention.
Embodiment 1:
The production of NCM811 material
A, nickel cobalt manganese NCM811 presoma Ni0.8Co0.1Mn0.1 (OH) 2 and lithium hydroxide raw material Li OH*H2O are taken, by Li
It is uniformly mixed with the ratio that M (NiCoMn sum total) molar ratio is 1.05:1.
B, leading portion rotary kiln is added in the material mixed, leads to nitrogen, burn 500 degrees Celsius, keep the temperature 3 hours.
C, inclination angle is adjusted, back segment rotary kiln is dumped into.Back segment kiln is passed through purity oxygen, is heated to 750 degrees Celsius, heat preservation 5 is small
When.
D, inclination angle discharging is adjusted, cools down, dispersed, sieve, pack in dry environments.
Embodiment 2:
The production of NCA material
D, nickel cobalt aluminium NCA presoma Ni0.8Co0.15Al 0.05 (OH) 2 and lithium hydroxide raw material Li OH*H2O are taken, by Li
It is uniformly mixed with the ratio that M (NiCoAl sum total) molar ratio is 1.04:1.
E, leading portion rotary kiln is added in the material mixed, leads to nitrogen, burn 500 degrees Celsius, keep the temperature 3 hours.
F, inclination angle is adjusted, back segment rotary kiln is dumped into.Back segment kiln is passed through purity oxygen, is heated to 750 degrees Celsius, heat preservation 5 is small
When.
D, inclination angle discharging is adjusted, cools down, dispersed, sieve, pack in dry environments.
Embodiment 3
Shown in Fig. 1, nickelic polynary positive pole material production rotary kiln comprising heating mantle 3, the interior setting of the heating mantle 3
There is rotary kiln inner tube 2, one end of the rotary kiln inner tube 2 is provided with feed inlet 1, the other end setting of the rotary kiln inner tube 2
There is discharge port 6;The bottom of the heating mantle 3 is provided with mounting seat 4 close to one end of feed inlet 1, close to one end of discharge port 6
It is provided with lifting inclination angle adjustor 5.
The raw material mixed put into leading portion rotary kiln from feed inlet 1, and adjustable inclination is level, are heated to 500 degrees Celsius,
Nitrogen protection is passed through from kiln tail.After heating 3 hours, fall lifting inclination angle adjustor 5, make in rotary kiln material by discharge port 6 from
So it is discharged into the feed inlet of back segment rotary kiln.
Back segment rotary kiln heating temperature is 680-780 degrees Celsius, is passed through oxygen.After logical oxygen heats 5 hours, stop heating,
Continue logical oxygen cooling, stops logical oxygen when being cooled to 500 degrees Celsius or less.Inclination angle is adjusted, discharging is carried out, obtains firing product.
Because nickelic ternary material is mostly using lithium hydroxide as lithium source material, in technical process, easy water suction causes to glue
Even, mixed effect is reduced, therefore uses two sections of burning methods, first so that mixed material is converted into oxidation state in first segment.
Exclude the influence and reaction of moisture of other atmosphere;Then the oxygen that reaction needs is passed through in second segment.
Energy consumption is greatly reduced in process of the invention, gas consumption is greatly decreased.Saggar carrying is burnt due to not using to hold,
And material is to stir at any time, is come into full contact with kiln atmosphere, so reaction speed is accelerated, gas consumption is greatly decreased, energy consumption also phase
It should reduce.
The nickelic polynary positive pole material structural stability of method production of the invention increases, and cycle life increases.Due to object
Material contacts sufficiently with oxygen atmosphere, and Lacking oxygen is effectively repaired and compensated in material structure, and material structure is more complete, in electrification
Cycle life increase is shown as during.
Method of the invention can extend service life of equipment.Since segmentation is burnt, shadow of the moisture in technical process is eliminated
It rings, therefore reduces the generation of corrosive gas, increase service life of equipment.
Finally, it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not intended to restrict the invention,
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features.
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in of the invention
Within protection scope.
Claims (4)
1. a kind of production method of nickelic polynary positive pole material, which is characterized in that it links by the way of rotary kiln sintered using two sections,
The firing process of nickelic polynary positive pole material is completed, the mode of traditional roller kilns and saggar carrying sintering is replaced.
2. the production method of nickelic polynary positive pole material according to claim 1, which is characterized in that in the rotary kiln
Chamber uses the high alumina ceramic material of resistance to oxidation under high temperature, and two sections of rotary kilns can freely adjust inclination angle;At inclination angle when level, to
It burns material and heats reaction in rotary kiln;When inclination angle is adjusted to 5 degree or more, rotary kiln carries out discharging.
3. the production method of nickelic polynary positive pole material according to claim 1, which is characterized in that leading portion kiln heating temperature
Range is 500~600 degrees Celsius, is passed through nitrogen from kiln tail in reaction process, forces air draft from kiln hood, control kiln inner pressure is micro-
Negative pressure;Back segment heating temperature range is 680 degree -780 and spends, and oxygen is passed through from kiln tail in reaction process, from kiln hood natural exhaust, kiln
Interior pressure is micro-positive pressure.
4. a kind of nickelic polynary positive pole material production rotary kiln, which is characterized in that including heating mantle, setting in the heating mantle
There is rotary kiln inner tube, one end of the rotary kiln inner tube is provided with feed inlet, and the other end of the rotary kiln inner tube, which is provided with, to be unloaded
Material mouth;The bottom of the heating mantle is provided with mounting seat close to one end of feed inlet, and one end close to discharge port is provided with liter
Inclination angle adjustor drops.
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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CN110444756A (en) * | 2019-08-19 | 2019-11-12 | 湖南金富力新能源股份有限公司 | The anode material for lithium-ion batteries and preparation method that are prepared with pyroreaction device and application |
CN110459759A (en) * | 2019-08-19 | 2019-11-15 | 湖南金富力新能源股份有限公司 | The anode material for lithium-ion batteries and its preparation method that are prepared with slewing equipment and application |
CN110530147A (en) * | 2019-07-30 | 2019-12-03 | 佛山市天禄智能装备科技有限公司 | A kind of high-temperature rotary furnace for the production of lithium battery anode high-nickel material continuous production |
CN112320857A (en) * | 2020-11-02 | 2021-02-05 | 中南大学 | Method for preparing ternary cathode material by split rotary kiln |
CN113686122A (en) * | 2021-08-12 | 2021-11-23 | 湖南烁科热工智能装备有限公司 | Continuous production rotary furnace for vanadium trioxide and use method thereof |
WO2023051503A1 (en) * | 2021-09-28 | 2023-04-06 | 宁夏中化锂电池材料有限公司 | Semi-finished positive electrode material, and preparation method and preparation device for positive electrode material |
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CN110530147A (en) * | 2019-07-30 | 2019-12-03 | 佛山市天禄智能装备科技有限公司 | A kind of high-temperature rotary furnace for the production of lithium battery anode high-nickel material continuous production |
CN110444756A (en) * | 2019-08-19 | 2019-11-12 | 湖南金富力新能源股份有限公司 | The anode material for lithium-ion batteries and preparation method that are prepared with pyroreaction device and application |
CN110459759A (en) * | 2019-08-19 | 2019-11-15 | 湖南金富力新能源股份有限公司 | The anode material for lithium-ion batteries and its preparation method that are prepared with slewing equipment and application |
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CN112320857A (en) * | 2020-11-02 | 2021-02-05 | 中南大学 | Method for preparing ternary cathode material by split rotary kiln |
CN113686122A (en) * | 2021-08-12 | 2021-11-23 | 湖南烁科热工智能装备有限公司 | Continuous production rotary furnace for vanadium trioxide and use method thereof |
WO2023051503A1 (en) * | 2021-09-28 | 2023-04-06 | 宁夏中化锂电池材料有限公司 | Semi-finished positive electrode material, and preparation method and preparation device for positive electrode material |
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