CN114284488B - Positive electrode material and determination method and application of stability of positive electrode material - Google Patents
Positive electrode material and determination method and application of stability of positive electrode material Download PDFInfo
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 110
- 238000000034 method Methods 0.000 title claims abstract description 57
- 238000000498 ball milling Methods 0.000 claims abstract description 80
- 229910021314 NaFeO 2 Inorganic materials 0.000 claims abstract description 4
- 230000001133 acceleration Effects 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 9
- 238000004364 calculation method Methods 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 64
- 238000002360 preparation method Methods 0.000 abstract description 22
- 230000008569 process Effects 0.000 abstract description 20
- 239000011267 electrode slurry Substances 0.000 abstract description 13
- 239000002002 slurry Substances 0.000 abstract description 10
- 238000003756 stirring Methods 0.000 abstract description 9
- -1 nickel cobalt aluminum Chemical compound 0.000 abstract description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 35
- 238000005245 sintering Methods 0.000 description 18
- 239000002243 precursor Substances 0.000 description 16
- 239000011324 bead Substances 0.000 description 15
- 239000013078 crystal Substances 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- 229910003002 lithium salt Inorganic materials 0.000 description 13
- 159000000002 lithium salts Chemical class 0.000 description 13
- 238000002156 mixing Methods 0.000 description 13
- 239000000843 powder Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 239000010405 anode material Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000010902 jet-milling Methods 0.000 description 9
- 238000011068 loading method Methods 0.000 description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 238000005054 agglomeration Methods 0.000 description 7
- 230000002776 aggregation Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000000227 grinding Methods 0.000 description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000005253 cladding Methods 0.000 description 4
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- 238000003825 pressing Methods 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
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- 230000007547 defect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000009775 high-speed stirring Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
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- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
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- 238000001704 evaporation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
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- 230000004048 modification Effects 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
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- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
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- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000000875 high-speed ball milling Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
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- 238000003466 welding Methods 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a positive electrode material, a judging method of stability of the positive electrode material and application of the positive electrode material. The positive electrode material is alpha-NaFeO 2 The structure is that the pH value of the positive electrode material before ball milling is m, the pH value after ball milling is n, n-m is less than or equal to 0.15, and the positive electrode material is nickel cobalt manganese or nickel cobalt aluminum ternary material, can be doped and can be coated. The positive electrode material provided by the invention has good stability and better processability and electrochemical performance when the pH value difference value is within a certain range before and after ball milling. The positive electrode material provided by the invention can not cause local gel due to the stirring and dispersing processes in the preparation process of the slurry in the preparation process of the positive electrode slurry, and the prepared positive electrode sheet has lower sheet resistance and lower direct current impedance. The method for judging the stability of the positive electrode material provided by the invention has higher accuracy, and the finally obtained result is very consistent with the stability matching degree of the positive electrode material.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a positive electrode material, a determination method of stability of the positive electrode material and application of the positive electrode material.
Background
Lithium ion batteries are the third generation of small-sized secondary batteries following nickel-cadmium batteries and nickel-hydrogen batteries. As a novel chemical power supply, the novel chemical power supply has the outstanding advantages of high working voltage, large specific energy, stable discharge potential curve, small self-discharge, long cycle life, good low-temperature performance, no memory, no pollution and the like, can meet the double requirements of people on small-size and light-weight batteries required by portable electric appliances and is beneficial to environmental protection, and is widely used for small-size electronic devices such as mobile communication, notebook computers, shooting and placing integrated machines and the like, and is also an ideal power supply for electric vehicles in the future.
With alpha-NaFeO 2 The ternary materials of lithium nickel cobalt manganese and lithium nickel cobalt aluminum with the structure become one of the main positive materials of the lithium ion power battery due to the higher gram capacity and excellent dynamic performance.
The positive electrode material may be cracked or broken during the preparation of the electrode slurry due to the stirring and dispersing process, and the cracking and breaking may occur in a single positive electrode material particle or may occur between a plurality of different particles. The newly generated positive electrode material interface after the cracks and the breakage are generated does not undergo passivation when being exposed to sintering atmosphere at high temperature, and does not undergo solid phase reaction with the coating element or is coated by the coating element. Therefore, on one hand, a large number of dangling bonds are easy to generate on the new interface, and protons are easy to be extracted from the slurry; on the other hand, lithium ions are easily separated from the lithium layer, so that the acid-base property of the slurry is affected. Because PVDF (polyvinylidene fluoride) is mostly used as the positive electrode of the current lithium ion battery, and is easy to crosslink under the condition of too high pH, the positive electrode material with too many cracks or easy to dissociate is extremely easy to generate local or whole gel near the cracks and the breaking areas in the slurry production process, so that uneven components are caused, uneven areas appear in the subsequent pole piece preparation, and even the subsequent processing cannot be performed at all.
Lithium salts such as lithium carbonate and lithium hydroxide are required in the production process of the ternary material. In order to obtain a product with more excellent performance, the sintering process in the production process often uses lithium salt with a stoichiometric ratio exceeding that of the sintering process so as to ensure that the final finished product cannot cause defects of low capacity, high impedance and the like due to the lack of lithium ions. Excess lithium salt remains on the surface of the ternary material, making the material alkaline. When preparing the positive electrode slurry, residual alkali on the surfaces can react with PVDF as a binder, so that partial or even whole gel is caused, and the positive electrode material, the binder and the conductive agent on the positive electrode plate are unevenly distributed, so that the subsequent battery manufacturing process cannot be carried out.
CN103392251a discloses a high nickel cathode material with low soluble alkali content, and the residual lithium salt on the surface of the material can be controlled to a certain extent by adjusting the manufacturing process, so as to achieve the purpose of regulating and controlling the alkalinity of the material. However, the dispersion of the positive electrode powder material is involved in the preparation of the positive electrode slurry, in which the materials are always under high-speed stirring, ball milling or collision. These processes can cause damage to the material such that the nascent surface of the material is exposed to the slurry, resulting in an increase in the alkalinity of the slurry, causing gelation.
CN107732199a discloses a fluorine-containing lithium ion battery positive electrode material, which is coated by a liquid phase coating and evaporating method, and the residual alkali on the surface is absorbed by a coating agent, but because the method is complex and inert gas is needed for protection in the evaporating process, if the residual alkali is high, the coating layer on the surface of the material is too thick, thereby affecting the performance of the material. Optimization for aqueous solutions is therefore a simple and low cost method of surface modification. LiOH and Li on the surface of the high-nickel positive electrode material can be washed by water 2 CO 3 And the lithium in the internal crystal lattice is dissolved into the aqueous solution after the material is washed by water in the washing process, so that the internal structure of the material is damaged, and the cycle performance of the material is seriously attenuated.
Therefore, how to improve the stability of the positive electrode material, so that the structure of the positive electrode material is not easily damaged in the process of preparing the positive electrode slurry, and the electrochemical performance of the material is improved is a technical problem to be solved.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a positive electrode material, a judging method of stability of the positive electrode material and application of the positive electrode material. The positive electrode material provided by the invention has good stability and better processability and electrochemical performance when the pH value difference value is within a certain range before and after ball milling. The positive electrode material provided by the invention can not cause local gel due to the stirring and dispersing processes in the preparation process of the slurry in the preparation process of the positive electrode slurry, and the prepared positive electrode sheet has lower sheet resistance and lower direct current impedance. The method for judging the stability of the positive electrode material provided by the invention has higher accuracy, and the finally obtained result is very consistent with the stability matching degree of the positive electrode material.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a positive electrode material, which is α -NaFeO 2 The pH value of the positive electrode material before ball milling is m, the pH value of the positive electrode material after ball milling is n, n-m is less than or equal to 0.15, for example, the n-m can be 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14 or 0.15 and the like;
the chemical general formula of the positive electrode material is Li a (Ni x Co y M 1-x-y ) 1-b M’ b O 2-c A c Wherein a is more than or equal to 0.85 and less than or equal to 1.2,0.5 and x is more than or equal to 0.85 and less than or equal to 1.2,0.5<1, 0.ltoreq.y.ltoreq.0.2, 0.ltoreq.b.ltoreq. 0.01,0.ltoreq.c.ltoreq.0.2, M comprises either Mn and/or Al, M' comprises either or a combination of at least two of Al, zr, ti, Y, sr, W or Mg, A comprises either or a combination of at least two of S, F or N, for example, the a may be 0.85, 0.9, 0.95, 1, 1.05, 1.1, 1.15 or 1.2, etc., the x may be 0.5, 0.6, 0.7, 0.8, 0.9 or 1, etc., the y may be 0, 0.05, 0.1, 0.15 or 0.2, etc., the b may be 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09 or 0.1, etc., and the c may be 0.02, 0.05, 0.08, 0.12.15, 0.18, 0.2, etc.
The pH value difference of the positive electrode material provided by the invention before and after ball milling is less than or equal to 0.15, the stability is good, and the material has better processability and electrochemical performance. The positive electrode material provided by the invention can not cause local gel due to the stirring and dispersing processes in the preparation process of the slurry in the preparation process of the positive electrode slurry, and the prepared positive electrode sheet has lower sheet resistance and lower direct current impedance.
According to the invention, the dispersion process of the material can be simulated by ball milling, and the occurrence condition of cracks and breakage in the process can be examined by the difference of pH values before and after ball milling, so that the difference of the pH values can well reflect the stability of the material.
Preferably, n-m is less than or equal to 0.1, such as 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, or the like.
In the invention, when the pH value difference of the positive electrode material before and after ball milling is further less than or equal to 0.1, the dissociation degree of the material particles is higher, and the broken soft agglomeration is less. The ternary positive electrode material with the characteristics can not generate a new interface in a long-term circulation process, and has good stability and high capacity retention rate.
Preferably, the ball milling time is 45-60 min, for example 45min, 46min, 47min, 48min, 49min, 50min, 51min, 52min, 53min, 54min, 55min, 56min, 57min, 58min, 59min or 60min, etc.
In the invention, the ball milling time is too short, so that the agglomerated crystal particles cannot be thoroughly broken, and the effect of detecting the agglomeration degree of the particles cannot be achieved. If the ball milling time is too long, single crystal particles may be cracked and broken, and the judgment result may be misled.
Preferably, in the ball milling, the acceleration of the ball milling is 65-75 m/s 2 For example 65m/s 2 、66m/s 2 、67m/s 2 、68m/s 2 、69m/s 2 、70m/s 2 、71m/s 2 、72m/s 2 、73m/s 2 、74m/s 2 Or 75m/s 2 Etc.
In the invention, the acceleration in the ball milling process is too small, so that the agglomerated crystal particles cannot be thoroughly broken, and the effect of detecting the agglomeration degree of the particles cannot be achieved. And the excessive acceleration can lead to breakage of monocrystalline particles and mislead the judgment result.
Preferably, in the ball milling, the volume-mass ratio of the ball milling beads and the positive electrode material is 200-250 mm 3 /g, e.g. 200mm 3 /g、205mm 3 /g、210mm 3 /g、215mm 3 /g、220mm 3 /g、225mm 3 /g、230mm 3 /g、235mm 3 /g、240mm 3 /g、245mm 3 /g or 250mm 3 /g, etc.
In the invention, the volume of the ball milling beads refers to the sum of the volumes of all the milling beads during ball milling. If the volume-mass ratio of the ball milling beads to the positive electrode material is too small, the agglomerated crystal particles cannot be thoroughly broken, and the effect of detecting the agglomeration degree of the particles cannot be achieved. The excessive mass ratio may cause breakage of monocrystalline particles and mislead the judgment result.
Preferably, the positive electrode material is a monocrystalline positive electrode material and/or a monocrystalline-like positive electrode material.
Preferably, the D50 of the positive electrode material is 2 to 4 μm, for example 2 μm, 2.2 μm, 2.5 μm, 2.8 μm, 3 μm, 3.2 μm, 3.5 μm, 3.8 μm or 4 μm, etc.
The median particle diameter of the positive electrode material provided by the invention is within the range of 1.5-4 mu m, and gram capacity exertion, direct current impedance and electrochemical stability can be considered. Excessive median particle diameter causes overlong diffusion path of lithium ions in particles, and affects gram volume exertion and impedance of materials; too small a median particle size results in a material with poor stability.
In a second aspect, the present invention provides a method for determining stability of the cathode material according to the first aspect, the method comprising:
and ball milling is carried out on the positive electrode material to obtain a pH value m before ball milling, the difference value of the pH values n and n-m after ball milling is used as a judging condition, and the stability of the positive electrode material is judged.
The ball milling provided by the invention is performed by adopting planetary ball milling equipment, including double planetary ball milling and the like.
In the invention, when the pH value difference (n-m) before and after ball milling is smaller than or equal to 0.15, the stability of the positive electrode material is better, and when the pH value difference (n-m) is larger than 0.15, the stability of the material is poorer, so that the processing performance of the material in positive electrode slurry and positive electrode pole pieces is influenced, and the electrochemical performance of a battery is further influenced.
The method can regulate and control the preparation method of the positive electrode material according to the judging method provided by the invention, such as regulating and controlling the sintering temperature, element doping or cladding amount, or crushing condition and the like in the preparation process of the positive electrode material through the pH value difference value of the positive electrode material obtained through judgment, not only can improve the stability of the material, but also can enable the growth of single crystals or single-crystal-like particles of the material to be more complete, namely the judging method provided by the method provides a good auxiliary effect for the preparation of the positive electrode material, and the positive electrode material with good stability and excellent electrochemical performance can be obtained through the judging method provided by the invention.
According to the method, the occurrence condition of cracking and breaking of the material can be well simulated through the ball milling process, and the pH value difference before and after ball milling can be used for investigation, so that the pH value difference can well reflect the stability of the material, and therefore, the stability judging method of the positive electrode material provided by the invention has high accuracy, and the finally obtained result is very consistent with the stability matching degree of the positive electrode material.
Preferably, the ball milling time is 45-60 min, for example 45min, 46min, 47min, 48min, 49min, 50min, 51min, 52min, 53min, 54min, 55min, 56min, 57min, 58min, 59min or 60min, etc.
In the invention, if the ball milling time is too short, the agglomerated crystal particles cannot be thoroughly broken, the effect of detecting the agglomeration degree of the particles cannot be achieved, and if the ball milling time is too long, the single crystal particles are possibly cracked and broken, and the judgment result is misled.
Preferably, in the ball milling, the acceleration of the ball milling is 65-75 m/s 2 For example 65m/s 2 、66m/s 2 、67m/s 2 、68m/s 2 、69m/s 2 、70m/s 2 、71m/s 2 、72m/s 2 、73m/s 2 、74m/s 2 Or 75m/s 2 Etc.
In the invention, if the acceleration in the ball milling process is too small, the agglomerated crystal particles cannot be thoroughly broken, the effect of detecting the agglomeration degree of the particles cannot be achieved, and if the acceleration is too large, the single crystal particles are possibly cracked and broken, and the judgment result is misled.
Preferably, the calculation formula of the acceleration of the ball mill is 4 ×pi 2 *r*f 2 And/3600, wherein r is the rotation radius of the ball mill, and f is the rotation speed of the ball mill.
Preferably, in the ball milling, the volume-mass ratio of the ball milling beads and the positive electrode material is 200-250 mm 3 /g, e.g. 200mm 3 /g、205mm 3 /g、210mm 3 /g、215mm 3 /g、220mm 3 /g、225mm 3 /g、230mm 3 /g、235mm 3 /g、240mm 3 /g、245mm 3 /g or 250mm 3 /g, etc.
Preferably, the calculation formula of the volume-mass ratio of the ball milling beads to the positive electrode material is 4/3 pi r 1 3 *n/m，r 1 And n is the number of ball milling balls, and m is the mass of the positive electrode material.
In the invention, the volume of the ball milling beads refers to the sum of the volumes of all the milling beads during ball milling. If the volume-mass ratio of the ball milling beads to the positive electrode material is too low, the agglomerated crystal particles cannot be thoroughly crushed, the effect of detecting the agglomeration degree of the particles cannot be achieved, and if the mass ratio is too high, the single crystal particles may be cracked and crushed, and the judgment result is misled.
As a preferable technical solution, the determination method includes:
the positive electrode material is processed at a speed of 65-75 m/s 2 Ball milling is carried out for 45-60 min to obtain the pH value before ball milling as m, the difference value of the pH value after ball milling as n, n-m is taken as a judging condition, and the stability of the positive electrode material is judged;
wherein, the calculation formula of the acceleration of the ball mill is g=4×pi 2 *r*f 2 R is the rotation radius of the ball mill, and f is the rotation speed of the ball mill; in the ball milling, the volume-mass ratio of ball milling balls to anode material is 200-250 mm 3 /g。
In a third aspect, the present invention also provides a lithium ion battery comprising the positive electrode material according to the first aspect.
Illustratively, the present invention provides a method for preparing the positive electrode material, which comprises:
ni is added with x Co y M 1-x-y (OH) 2 Precursor bodyMixing with lithium salt (doping or cladding can be carried out), then heating and sintering, breaking jaw after sintering, and carrying out jet milling to obtain the anode material.
Ni x Co y M 1-x-y (OH) 2 The particle size and specific surface area of the precursor are not particularly limited, but in order to obtain a relatively good morphology of single crystal or single crystal-like, it is recommended to use a particle size satisfying the volume distribution 50% integrated value Dv50 of 2 to 7 μm and a specific surface area of 5 to 15m 2 Per gram of small particle precursor.
The lithium salt may be lithium carbonate or lithium hydroxide, and the molar ratio of the lithium salt to the precursor may be set to 0.95 to 1.1.
Other doping coating elements may be added during mixing, typically in the form of oxides. Such as zirconia, yttria, alumina, titania, magnesia, and the like. The mass ratio of the oxide corresponding to the non-oxygen element to the precursor is recommended to be 50-10000 ppm.
The mixing equipment used in mixing the precursor and the lithium salt can be a high-speed mixer or a coulter, and the mixing requires that all the mixed substances have a difference of <3% when the mass percentage of each element is compared by 4 random sampling.
The equipment used for the temperature-rising sintering needs to realize the function of temperature control and gas flow control. The form of the kiln can be a box type furnace or a roller kiln, and the roller kiln is generally recommended. And loading the mixed precursor, lithium salt and doping cladding agent into a sagger, and feeding the sagger into a furnace body to finish sintering.
The rate of temperature rise during sintering is not particularly required. In order to uniformly and jointly heat the precursor and the lithium salt and the doping coating agent loaded in the sagger, a heating rate of 3-10 ℃/min is recommended. Air or oxygen can be introduced into the furnace body in the heating stage to help discharge gas products such as water, carbon dioxide and the like generated by the reaction.
The constant temperature used in sintering depends on the ratio of the materials and the performance requirements of the materials. For materials with x being less than or equal to 0.5 and less than or equal to 0.75, the constant temperature is recommended to be selected within the range of 900-1200 ℃; for a material of 0.75< x <1, the constant temperature is recommended to be selected in the range of 750-1050 ℃. The sintering time at constant temperature is recommended to be 4-12 hours, and air or oxygen can be introduced into the furnace body at constant temperature stage to help discharge the gaseous products such as water, carbon dioxide and the like generated by the reaction.
The material block obtained after sintering is crushed by an air flow mill or a disc mill after jaw breaking. The air pressure and the frequency of the classifying wheel of the air flow mill are regulated so as to realize the crushing and the grain diameter control of the sintered materials. The recommended air pressure selection range is 0.2-0.9 MPa, and the grading wheel frequency is 20-50 rpm. If the proper particle size is larger than the particle size obtained by crushing, the air pressure used by the jet mill or the frequency of the classifying wheel should be reduced; if the suitable particle size is smaller than the resulting particle size, the air pressure or classifying wheel frequency used by the jet mill should be increased. The appropriate particle size and degree of crushing of the corresponding sintered material can be determined by the ball milling method described below in this patent.
Multiple sintering can be performed to obtain ternary positive electrode materials with more excellent performance. Taking the second sintering as an example, the product after the first sintering and crushing can be mixed with doping or cladding agents, and then kept at the constant temperature of 500-1000 ℃ for 3-10 hours. The specific conditions of the temperature rising rate and the gas charging are the same as those of the first sintering. An appropriate amount of lithium salt (the molar ratio of the lithium salt and the primary sintered product is recommended to be controlled between 0.5 and 1%) can be added simultaneously and mixed before secondary sintering. After sintering, the anode material can be directly packaged or subjected to one-round airflow crushing according to the properties of the material, and the anode material is obtained by adjusting the crushing parameters of an airflow mill.
Compared with the prior art, the invention has the following beneficial effects:
the positive electrode material provided by the invention has good stability and better processability and electrochemical performance when the pH value difference value is within a certain range before and after ball milling. The positive electrode material provided by the invention can not cause local gel due to the stirring and dispersing processes in the preparation process of the slurry in the preparation process of the positive electrode slurry, and the prepared positive electrode sheet has lower sheet resistance and lower direct current impedance. According to the battery provided by the invention, the diaphragm resistance of the positive electrode plate is as low as 769mΩ or less, the cell DCR is 8.7 Ω or less, the ball milling time is controlled within 45-60 min, the diaphragm resistance of the positive electrode plate is as low as 541mΩ or less, and the cell DCR is 6.5 Ω or less. The method for judging the stability of the positive electrode material provided by the invention has higher accuracy, and the finally obtained result is very consistent with the stability matching degree of the positive electrode material.
Detailed Description
The technical scheme of the invention is further described by the following specific examples. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
In a specific embodiment, the present invention provides a method for determining stability of a cathode material, the method comprising:
the positive electrode material is processed at a speed of 65-75 m/s 2 Ball milling is carried out for 45-60 min to obtain the pH value before ball milling as m, the difference value of the pH value after ball milling as n, n-m is taken as a judging condition, and the stability of the positive electrode material is judged;
wherein, the calculation formula of the acceleration of the ball mill is g=4×pi 2 *r*f 2 R is the rotation radius of the ball mill, and f is the rotation speed of the ball mill; in the ball milling, the volume-mass ratio of ball milling balls to anode material is 200-250 mm 3 /g。
Example 1
This example provides a positive electrode material (D50 of 2 μm) having a chemical formula shown in table 1 and a difference value of n-m shown in table 1 after the positive electrode material was subjected to the determination method of the above embodiment.
The ball milling conditions are as follows:
in the embodiment, PM100 equipment of Leachi company is selected, 9 zirconia grinding beads with the diameter of 10mm are added into a material tank, and 20g of positive electrode material, namely the volume-mass ratio of the ball grinding beads to the positive electrode material is 235.5mm 3 /g, run at 300rpm for 60min. The diameter of the sun gear of the equipment is 0.141m, and the calculated ball milling acceleration g is 69.5m/s 2 。
The preparation method of the positive electrode material provided by the embodiment is as follows:
ni is selected for 0.6 Co 0.1 M 0.3 (OH) 2 Precursor, dv50=3.5 μm, specific surface 9m 2 And/g. Mixing with lithium carbonate in a molar ratio of 1:1.05, adding 0.12wt% (relative to the precursor) of nanoscale ZrO 2 The powder is mixed uniformly in a high-speed mixer. After loading into the sagger, the temperature is raised to 930 ℃ at a temperature rise rate of 5 ℃/min and maintained for 8 hours. After the material block is cooled, the material block enters an air flow mill to be crushed through jaw breaking. The parameters of the jet milling were set to 0.7MPa, the classifier wheel frequency 40rpm. Dv50=2 μm of the material after the pulverization was completed. Mixing the material with 0.15wt% of nano Al 2 O 3 The powder was mixed uniformly using a high-speed mixer, and after loading into a sagger, the temperature was raised to 550℃at a heating rate of 10℃per minute and maintained for 5 hours. And directly packaging the cooled powder without jet milling to obtain the finished product anode material.
Example 2
This example provides a positive electrode material (D50 of 3.2 μm) having a chemical formula shown in table 1 and a difference value of n-m shown in table 1 after the positive electrode material was subjected to the determination method of the above embodiment.
The ball milling conditions are as follows:
in the embodiment, PM100 equipment of Leachi company is selected, 10 zirconia grinding beads with the diameter of 10mm are added into a material tank, and 21g of positive electrode material, namely the volume-mass ratio of the ball grinding beads to the positive electrode material is 250mm 3 /g, operating at a speed of 350rpm for 45min. The diameter of the sun gear of the equipment is 0.141m, and the calculated ball milling acceleration g is 69.5m/s 2 。
The preparation method of the positive electrode material provided by the embodiment is as follows:
ni is selected for 0.6 Co 0.1 M 0.3 (OH) 2 Precursor, dv50=3.5 μm, specific surface 9m 2 And/g. Mixing with lithium carbonate in a molar ratio of 1:1.05, adding 0.12wt% (relative to the precursor) of nanoscale ZrO 2 The powder is mixed uniformly in a high-speed mixer. After loading into the sagger, the temperature is raised to 940 ℃ at a temperature rising rate of 5 ℃/min and maintained for 8 hours. After the material block is cooled, the material block enters an air flow mill to be crushed through jaw breaking. The parameters of the jet milling are set to be 0.5MPa, and the classifying wheelThe frequency was 35rpm. Dv50=3.2 μm of the material after the pulverization was completed. Mixing the material with 0.15wt% of nano Al 2 O 3 The powder was mixed uniformly using a high-speed mixer, and after loading into a sagger, the temperature was raised to 550℃at a heating rate of 10℃per minute and maintained for 5 hours. And directly packaging the cooled powder without jet milling to obtain the finished product anode material.
Example 3
This example provides a positive electrode material (D50 of 4 μm) having a chemical formula shown in table 1 and a difference value of n-m shown in table 1 after the positive electrode material was subjected to the determination method of the above embodiment.
The ball milling conditions are as follows:
in the embodiment, PM100 equipment of Leachi company is selected, 8 zirconia grinding beads with the diameter of 10mm are added into a material tank, and 20.5g of positive electrode material, namely the volume mass ratio of the ball grinding beads to the positive electrode material is 204.3mm 3 The/g was run at 300rpm for 50min. The diameter of the sun gear of the equipment is 0.141m, and the calculated ball milling acceleration g is 69.5m/s 2 。
The preparation method of the positive electrode material provided by the embodiment is as follows:
ni is selected for 0.6 Co 0.1 M 0.3 (OH) 2 Precursor, dv50=3.5 μm, specific surface 9m 2 And/g. Mixing with lithium carbonate in a molar ratio of 1:1.05, adding 0.12wt% (relative to the precursor) of nanoscale ZrO 2 The powder is mixed uniformly in a high-speed mixer. After loading into the sagger, the temperature is raised to 980 ℃ at a temperature rise rate of 5 ℃/min and maintained for 8 hours. After the material block is cooled, the material block enters an air flow mill to be crushed through jaw breaking. The parameters of the jet milling were set to 0.4MPa, the classifier wheel frequency was 30rpm. Dv50=3.2 μm of the material after the pulverization was completed. Mixing the material with 0.15wt% of nano Al 2 O 3 The powder was mixed uniformly using a high-speed mixer, and after loading into a sagger, the temperature was raised to 550℃at a heating rate of 10℃per minute and maintained for 5 hours. And directly packaging the cooled powder without jet milling to obtain the finished product anode material.
Example 4
The difference between this example and comparative example 1 is that the ball milling time in this example was 30min.
The conditions and process for the preparation of the remaining materials remain the same as in comparative example 1.
Example 5
The difference between this example and example 1 is that the ball milling time in this example was 75min.
The conditions and process for the preparation of the remaining materials remain the same as in example 1.
Comparative example 1
The difference between this comparative example and example 1 is that the pH n-m of the positive electrode material in this comparative example is 0.2.
The ball milling conditions and method were the same as in example 1.
The preparation method of the positive electrode material provided by the embodiment is as follows:
ni is selected for 0.6 Co 0.1 M 0.3 (OH) 2 Precursor, dv50=3.5 μm, specific surface 9m 2 And/g. Mixing with lithium carbonate in a molar ratio of 1:1.05, adding 0.12wt% (relative to the precursor) of nanoscale ZrO 2 The powder is mixed uniformly in a high-speed mixer. After loading into the sagger, the temperature is raised to 930 ℃ at a temperature rise rate of 5 ℃/min and maintained for 8 hours. After the material block is cooled, the material block enters an air flow mill to be crushed through jaw breaking. The parameters of the jet milling were set to 0.4MPa, the classifier wheel frequency was 30rpm. Dv50=3.6 μm of the material after the pulverization was completed. Mixing the material with 0.15wt% of nano Al 2 O 3 The powder was mixed uniformly using a high-speed mixer, and after loading into a sagger, the temperature was raised to 550℃at a heating rate of 10℃per minute and maintained for 5 hours. And directly packaging the cooled powder without jet milling to obtain the finished product anode material.
The positive electrode materials provided in examples 1-5 and comparative example 1 were mixed with carbon black as a conductive agent and PVDF as a binder in a ratio of 97:1.7:1.3 and added to NMP as an organic solvent and stirred at high speed to form a uniform dispersion; and after the high-speed stirring is finished, negative pressure defoaming is performed in a stirring tank, so that the anode slurry suitable for coating is obtained. And coating the obtained positive electrode slurry on an aluminum foil through a transfer coater, and drying, cold pressing and slitting to prepare the positive electrode plate with the required shape. Controlling the compacted density of the positive electrode active material coating region to be 3.4g/cm during cold pressing 3 Within the inner part.
Mixing a negative electrode active material with carbon black as a conductive agent, a binder and CMC according to the proportion of 96.8:1.2:1.2:0.8, and adding the mixture into deionized water to be stirred at a high speed to form uniform dispersion liquid; and after the high-speed stirring is finished, negative pressure defoaming is carried out in a stirring tank, so that the negative electrode slurry suitable for coating is obtained. And (3) coating the obtained negative electrode slurry on a copper foil through a transfer coater, and drying, cold pressing and slitting to obtain the negative electrode plate with the required shape. Controlling the compacted density of the anode active material coating region to be 1.6g/cm during cold pressing 3 Within the inner part.
And placing the positive and negative plates on two sides of the isolating film and winding to form a winding core, and connecting the reserved uncoated area with the nickel tab through ultrasonic welding. The roll core is wrapped by an aluminum plastic film and then is heat-sealed, and one side is reserved for liquid injection.
13wt% LiPF is added to a mixed solvent of EC: EMC: DEC=3:5:2 6 1wt% of vinylene carbonate and 2wt% of DTD are used as lithium salt and additives to prepare electrolyte, and the electrolyte is injected into an aluminum plastic film wrapped with a winding core. And then vacuum packaging, standing and forming to obtain the lithium ion battery.
The batteries provided in examples 1-5 and comparative example 1 were tested under the following conditions:
pH test: the measurement was performed using a pH meter, which was calibrated for later use, and then 5g of a single sample was accurately weighed and placed in a 100ml beaker. 45g of deionized water is added, a magnetic rotor is placed in a beaker, the whole fresh-keeping film is sealed to isolate air, and the beaker is placed on a magnetic stirrer to be stirred for 30min. The temperature was maintained at 25℃throughout the process. And after stirring, the supernatant is not required to be taken out, the probe of the pH meter is cleaned and then wiped dry, the probe is inserted into the supernatant of the solution through a preservative film, and the mouth of the beaker is sealed by the preservative film to isolate air for testing, so that the pH value is obtained. The test was repeated three times and the average was taken.
And (3) testing the resistance of the membrane: the pressure was set at 25kg and the dwell time was 400s using the Yuan energy technology BER 2500. And placing the pole piece after coating and drying between two probes of the equipment, and using the equipment to operate and measure by using self-contained software to obtain the conductivity of the pole piece.
DCR test: the SOC state of the battery was adjusted to 50% (i.e., charged from the fully discharged state of the battery to 50% of the rated capacity) at a rate of 0.33C (i.e., 0.33 times the rated capacity of the battery was set as the current magnitude) using a charge-discharge apparatus, the battery was left to stand for 30 minutes, then operated at a constant current a of 3C, and the voltage change Δv during discharge was recorded, and dcr=Δv/a.
The chemical formulas of the positive electrode materials of examples 1 to 5 and comparative example 1, before ball milling (i.e., initial) pH, ball milling time, pH after ball milling, n-m values, and the sheet resistance of the positive electrode sheet and DCR of the cell, respectively, are shown in table 1.
TABLE 1
As can be seen from the data in examples 1 and 4, the ball milling time is too short, and a large amount of unopened soft agglomerates still exist in the material, so that the defect of poor material stability cannot be reflected even if the difference of pH values is small.
From the data of examples 1 and 5, it is clear that the ball milling time is too long, and the whole single crystal particles of the material are cracked and damaged, which may result in large pH value change and misjudgment on the stability of the material.
As can be seen from the data results of the example 1 and the comparative example 1, when the difference of n-m before and after ball milling is too large in the positive electrode material, the stability of the material is poor, the resistance of the pole piece membrane prepared by the same method is obviously increased, and the DCR of the battery is higher.
In conclusion, the positive electrode material provided by the invention has good stability and better processability and electrochemical performance when the pH value difference value is within a certain range before and after ball milling. The positive electrode material provided by the invention can not cause local gel due to the stirring and dispersing processes in the preparation process of the slurry in the preparation process of the positive electrode slurry, and the prepared positive electrode sheet has lower sheet resistance and lower direct current impedance. According to the battery provided by the invention, the diaphragm resistance of the positive electrode plate is as low as 769mΩ or less, the cell DCR is 8.7 Ω or less, the ball milling time is controlled within 45-60 min, the diaphragm resistance of the positive electrode plate is as low as 541mΩ or less, and the cell DCR is 6.5 Ω or less. The method for judging the stability of the positive electrode material provided by the invention has higher accuracy, and the finally obtained result is very consistent with the stability matching degree of the positive electrode material.
The applicant states that the detailed method of the present invention is illustrated by the above examples, but the present invention is not limited to the detailed method described above, i.e. it does not mean that the present invention must be practiced in dependence upon the detailed method described above. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (2)
1. A method for determining stability of a positive electrode material, the method comprising:
the positive electrode material is processed at 65-75 m/s 2 Ball milling is carried out for 45-60 min to obtain the pH value before ball milling as m, the difference value of the pH value after ball milling as n, n-m is taken as a judging condition, and the stability of the positive electrode material is judged;
wherein the calculation formula of the acceleration of the ball mill is 4 pi 2 *r*f 2 R is the rotation radius of the ball mill, and f is the rotation speed of the ball mill; in the ball milling, the volume-mass ratio of ball milling balls to positive electrode material is 200-250 mm 3 /g；
The positive electrode material is alpha-NaFeO 2 The pH value of the positive electrode material before ball milling is m, and the pH value after ball milling is n, wherein n-m is less than or equal to 0.15;
the chemical general formula of the positive electrode material is Li a (Ni x Co y M 1-x-y ) 1-b M’ b O 2-c A c Wherein a is more than or equal to 0.85 and less than or equal to 1.2,0.5 and x is more than or equal to 0.85 and less than or equal to 1.2,0.5<Y is more than or equal to 1 and less than or equal to 0.2, b is more than or equal to 0 and less than or equal to 0.01,0, c is more than or equal to 0.2, M comprises Mn and/or Al, and M' comprisesAl, zr, ti, Y, sr, W or Mg, a comprises S, F or N, or a combination of at least two; the positive electrode material is a monocrystalline positive electrode material and/or a monocrystalline-like positive electrode material.
2. The method for determining the stability of a positive electrode material according to claim 1, wherein the D50 of the positive electrode material is 2 to 4 μm.
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