CN106784675B - A kind of dry method method for coating of anode material of lithium battery - Google Patents
A kind of dry method method for coating of anode material of lithium battery Download PDFInfo
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- CN106784675B CN106784675B CN201611170130.5A CN201611170130A CN106784675B CN 106784675 B CN106784675 B CN 106784675B CN 201611170130 A CN201611170130 A CN 201611170130A CN 106784675 B CN106784675 B CN 106784675B
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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
- H01M4/362—Composites
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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
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Abstract
The invention belongs to lithium ion battery material technical fields, more particularly to a kind of dry method method for coating of anode material of lithium battery, after coating to mix with boric acid to pretreatment, it mixes and fires with positive electrode, obtain the finished product of positive electrode, this method makes required covering material and contact agent form solid solution, it is easy to be evenly coated, and it is tightly combined after firing, clad is not easily to fall off, the method not only shortens the production cycle, and it ensure that the uniformity of cladding, make covering material that can also form ideal glassy state cladding by high temperature, improve the performance of material.
Description
Technical field
The invention belongs to lithium ion battery material technical fields more particularly to a kind of dry method of anode material of lithium battery to coat
Method.
Background technique
Important raw material of the positive electrode of lithium ion battery as lithium secondary battery, restricts it in power lithium-ion battery
The main difficult technical of aspect application is that its high-temperature cycle life is undesirable.Positive electrode can be extenuated and be solved to cladding process
Most of problem.
Traditional cladding process is mainly liquid phase coating, i.e., positive electrode firing after, using liquid phase covering material into
Then row cladding makes coating be stable at material surface with drying or simple resintering again.The shortcomings that this kind of technique, is more obvious: first
First, most of covering materials are hardly formed liquid phase, i.e. the alternative coating of the method is less；Secondly, after liquid phase coating
During being fired again, destructible clad makes cladding generate defect；Third, the process effects material of cladding
Performance；4th, the integrated artistic period is longer, and production efficiency is lower.
In view of the above shortcomings, the designer, is actively subject to research and innovation, to found a kind of anode material of lithium battery
Dry method method for coating, make it with more the utility value in industry.
Summary of the invention
In order to solve the above technical problems, the object of the present invention is to provide a kind of dry method cladding sides of anode material of lithium battery
Method, required covering material and contact agent form solid solution, are easy to be evenly coated, and are tightly combined after firing, and clad is not easy
It falls off, the method not only shortens the production cycle, but also ensure that the uniformity of cladding, makes covering material that can also pass through high temperature
To form ideal glassy state cladding, the performance of material is improved.
A kind of dry method method for coating of anode material of lithium battery proposed by the present invention, comprising the following steps:
S1. coating is pre-processed: coating is oxide, and size distribution D50 is made less than 3 μm using boric acid
For contact agent, by boric acid with oxide by weight 1:(2~3) it mixes, before cladding process in 2 hours, in ten thousand turns of high speed powder
It is crushed 5~10 seconds in broken machine, makes its surface active, state is fluffy；
S2. it will pass through pretreated coating in pre-burning or the positive electrode being burnt into and the step S1 according to mass ratio
(100~50): 1 is uniformly mixed in batch mixer；
S3. in atmospheric conditions, the material mixed in the step S2 is fired, is warming up to 765 DEG C~935
DEG C, 5~16h is kept the temperature, obtains product after cooling.
Further, the oxide in the step S1 is aluminium oxide or titanium dioxide, and D50 is 1 μm.
According to the above aspect of the present invention, the present invention has at least the following advantages: the present invention is coated using dry method, makes required cladding material
Material forms solid solution with contact agent, is easy to be evenly coated, and is tightly combined after firing, and clad is not easily to fall off, and the method is not only
The production cycle is shortened, and ensure that the uniformity of cladding, form covering material can also by high temperature ideal
Glassy state cladding, improves the performance of material.
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention,
And can be implemented in accordance with the contents of the specification, the following is a detailed description of the preferred embodiments of the present invention and the accompanying drawings.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of finished product in the embodiment of the present invention 1；
Fig. 2 is the charge and discharge cycles curve graph of finished product in the embodiment of the present invention 1；
Fig. 3 is the scanning electron microscope (SEM) photograph of finished product in the embodiment of the present invention 2.
Specific embodiment
With reference to the accompanying drawings and examples, specific embodiments of the present invention will be described in further detail.Implement below
Example is not intended to limit the scope of the invention for illustrating the present invention.
Embodiment 1
Lithium manganate material dry method coated aluminum oxide
S1. by weight, 2 parts of nano alumina powder (about 1 micron of D50) is taken, 1 part of boric acid, is placed in ten thousand turns of high speed powder jointly
It in broken machine, crushes 10 seconds, takes out spare；
S2. LiMn2O4 semi-finished product to be covered and above-mentioned coating are put in proportion into V-type batch mixer, coating and mangaic acid
The weight ratio of lithium is 1:80, is uniformly mixed；
S3. to guarantee being evenly coated property and effect, polyurethane ball is added in the mixture, is 1:3's in ball material weight ratio
Under the conditions of, mixed on low speed 2 hours or more；
S4. mixed material is fired, firing process parameter are as follows: 850 DEG C of heat preservation 10h are warming up to, it is cooling, complete packet
It covers, temperature involved by the firing process parameter can fluctuate 10% up and down；
S5. by the material merging high speed mixer for completing cladding process, (1400 revs/min) of high speed is opened and mixes 1 point
Clock carries out subsequent removal of impurities, screening, packaging.
The scanning electron microscope (SEM) photograph of finished product obtained in this implementation is shown in Fig. 1, from the figure, it can be seen that the colony size of finished-product material
(i.e. granule size) controllably, gap of the coating between grain surface and colony is distributed, in integral material scanning process
More uniformly；Finished product is at 55 DEG C of high temperature, multiplying power 1C, and charge and discharge voltage is that the charge-discharge cycle curve of 3.0V~4.3V is shown in Fig. 2, from figure
In it can be seen that, the capacity retention ratio of the finished product is 82%, and the material compared to produced in conventional processes improves significantly.
Embodiment 2
Nickel-cobalt lithium manganate material dry method cladding titanium dioxide
S1. by weight, 3 parts of nano-titanium dioxide (about 1 micron of D50) is taken, 1 part of boric acid, is placed in ten thousand turns of high speed powder jointly
It in broken machine, crushes 5 seconds, takes out spare；
S2. nickle cobalt lithium manganate semi-finished product to be covered and above-mentioned coating are put in proportion into high-speed mixer, coating
Weight ratio with nickle cobalt lithium manganate is 1:100, opens (1400 revs/min) of high speed and mixes 15 minutes；
S3. mixed material is fired, firing process parameter are as follows: 800 DEG C of heat preservation 8h are warming up to, it is cooling, complete packet
It covers, temperature involved by the firing process parameter can fluctuate 10% up and down；
S4. by the material merging high speed mixer for completing cladding process, (1400 revs/min) of high speed is opened and mixes 1 point
Clock carries out subsequent removal of impurities, screening, packaging.
The scanning electron microscope (SEM) photograph of finished product obtained in this implementation is shown in Fig. 3, from the figure, it can be seen that the colony size of finished-product material
(i.e. granule size) controllably, gap of the coating between grain surface and colony is distributed, in integral material scanning process
More uniformly.
In conclusion dry method cladding process of the present invention using contact agent fusion coating, feature are (excellent using contact agent
It is selected as boric acid) it is mixed jointly with fine grain coating, it pre-processes, then cladding is mixed with the positive electrode being wrapped by.Boric acid is normal
It is solid that temperature is lower, and matter is soft, and being twisted with finger can crush, and can mix with many kinds of solids and liquid, and micro mist shape boric acid is easy to absorb water
Agglomeration, but can be crushed easily, boric acid is decomposed into water and boron oxide under high temperature, and can form liquid phase, is good contact agent choosing
Select, coating can be made evenly dispersed, be unlikely to due to surface can it is larger and generate reunion, and boric acid can be evenly distributed in by
It coats on substance, so that the coating of attachment be made also to be uniformly distributed.
The invention has the following advantages that A, covered effect are more preferably, due to coating material at high temperature with boric acid form at
Liquid phase, this makes coating that can not only be uniformly distributed in positive electrode particle surface, more makes it combine power enhancing, makes after cooling
Clad is more stable, and covered effect is more preferably.B, selectable coating is all kinds of increases, since contact agent boric acid is loose at normal temperature
It is soft, it can be uniformly dispersed with cladding substance by simple and mechanical mixed packet, so regardless of whether soluble coating can be used,
And become boric acid at high temperature, after boric acid volatilization aqueous vapor and do, liquid phase solid solution can be formed with coating, so that the dispersion of coating
More thoroughly, be more evenly distributed, mix cladding using coating and main raw material, rather than with finished-product material or pre-burning object
Mixing cladding, improves the combination degree of covering material and lithium manganate material, keeps cladding more stable effectively.C, selectable packet
Time freedom is covered, is played convenient for integrated artistic, may be selected after firing to coat cladding process again, also can choose pre-
It is coated after burning, before firing, is selected according to different process conditions.Resource and the energy can be saved to avoid iterative process,
Pyroprocess needed for coating and material pass through sintering reaction jointly makes coating not only can be on the colony surface that material is formed
Cladding is formed, while also forming cladding in biggish gap in colony, keeps covered effect even more ideal and perfect.D, exempt wet
Method mixing, it is more environmentally friendly, it more saves, low cost.Due to not needing to introduce liquid phase process, drawing for complicated chemical substance is avoided
Enter, so that technical process is more environmentally friendly, more saves, cost is greatly reduced.E, contact agent has the function of improving grain morphology: due to
It using boric acid as contact agent, can make during cladding, form liquid-phase sintering, there is certain modification to material grains pattern
Effect.The specific surface area of material is can be controlled within 0.5 every gram of square meter, and the high temperature cyclic performance for improving material has significant
Effect.
The above is only a preferred embodiment of the present invention, it is not intended to restrict the invention, it is noted that for this skill
For the those of ordinary skill in art field, without departing from the technical principles of the invention, can also make it is several improvement and
Modification, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (1)
1. a kind of dry method method for coating of anode material of lithium battery, it is characterised in that: the following steps are included:
S1. coating is pre-processed: coating is oxide, and size distribution D50 is used as using boric acid and is connect less than 3 μm
Agent is touched, by boric acid with oxide by weight 1:(2~3) it mixes, before cladding process in 2 hours, in ten thousand turns of high speed disintegrators
It is middle to crush 5~10 seconds, make its surface active, state is fluffy；
S2. it will pass through pretreated coating in pre-burning or the positive electrode being burnt into and the step S1 according to mass ratio (100
~50): 1 is uniformly mixed in batch mixer；
S3. in atmospheric conditions, the material mixed in the step S2 is fired, is warming up to 765 DEG C~935 DEG C, protected
5~16h of temperature obtains product after cooling；
Oxide in the step S1 is aluminium oxide or titanium dioxide, and D50 is 1 μm.
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| CN107248575A (en) * | 2017-07-19 | 2017-10-13 | 苏州思创源博电子科技有限公司 | A kind of preparation method of titanium-oxide-coated lithium manganate material |
| CN107302086A (en) * | 2017-07-19 | 2017-10-27 | 苏州思创源博电子科技有限公司 | A kind of preparation method of titanium-oxide-coated sodium ion tertiary cathode material |
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| CN107425188A (en) * | 2017-07-30 | 2017-12-01 | 苏州思创源博电子科技有限公司 | A kind of preparation method of oxide cladding lithium cobaltate cathode material |
| CN107226455A (en) * | 2017-08-05 | 2017-10-03 | 苏州思创源博电子科技有限公司 | A kind of niobium is modified the preparation method of lithium cobaltate cathode material |
| CN107394181A (en) * | 2017-08-05 | 2017-11-24 | 苏州思创源博电子科技有限公司 | A kind of niobium is modified sodium-ion battery positive material preparation method |
| CN107492646A (en) * | 2017-08-11 | 2017-12-19 | 苏州思创源博电子科技有限公司 | A kind of preparation method of the sulphur lithium anode material of carbon silicon cladding |
| CN107317020A (en) * | 2017-08-13 | 2017-11-03 | 苏州思创源博电子科技有限公司 | A kind of preparation method of cladded type sodium ion tertiary cathode material |
| CN107293696A (en) * | 2017-08-13 | 2017-10-24 | 苏州思创源博电子科技有限公司 | A kind of preparation method of compound manganese lithium anode material |
| CN111952547A (en) * | 2019-05-16 | 2020-11-17 | 天津国安盟固利新材料科技股份有限公司 | Surface-coated modified lithium ion battery positive electrode material and preparation method thereof |
| CN111952552B (en) * | 2019-05-17 | 2021-11-30 | 湖南杉杉能源科技股份有限公司 | Glass state coated positive electrode material and preparation method thereof |
| TWI761920B (en) * | 2019-08-27 | 2022-04-21 | 德商贏創運營有限公司 | Mixed lithium transition metal oxide containing pyrogenically produced zirconium-containing oxides |
| CN111276691A (en) * | 2020-03-24 | 2020-06-12 | 江门市科恒实业股份有限公司 | High-voltage single-crystal low-cobalt ternary cathode material and preparation method thereof |
| CN112133917B (en) * | 2020-09-09 | 2021-11-26 | 天津巴莫科技有限责任公司 | Preparation method and application of cobalt-free composite material with spinel structure and layered structure |
| CN113903895B (en) * | 2021-09-27 | 2023-03-03 | 蜂巢能源科技有限公司 | Coating method of cobalt-free positive electrode material, cobalt-free positive electrode material and lithium ion battery |
| CN114400330B (en) * | 2022-03-23 | 2022-07-12 | 湖南长远锂科新能源有限公司 | Al/B co-coated positive electrode material and preparation method thereof |
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Address after: 214000 Gangxia Wuxing Industrial Park, Donggang Town, Xishan District, Wuxi City, Jiangsu Province Patentee after: WUXI JEWEL POWER & MATERIALS Co.,Ltd. Address before: 214000 Gangxia Wuxing Industrial Park, Donggang Town, Xishan District, Wuxi City, Jiangsu Province Patentee before: WUXI JEWEL POWER & MATERIALS Co.,Ltd. |
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