CN114284488A - Positive electrode material, and determination method and application of stability thereof - Google Patents
Positive electrode material, and determination method and application of stability thereof Download PDFInfo
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 54
- 238000000498 ball milling Methods 0.000 claims abstract description 94
- 239000010406 cathode material Substances 0.000 claims abstract description 37
- 239000010405 anode material Substances 0.000 claims abstract description 25
- 229910006525 α-NaFeO2 Inorganic materials 0.000 claims abstract description 4
- 229910006596 α−NaFeO2 Inorganic materials 0.000 claims abstract description 4
- 239000011324 bead Substances 0.000 claims description 22
- 239000013078 crystal Substances 0.000 claims description 18
- 230000001133 acceleration Effects 0.000 claims description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229910004150 O2-cAc Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 229910052719 titanium 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
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 69
- 238000002360 preparation method Methods 0.000 abstract description 24
- 230000008569 process Effects 0.000 abstract description 19
- 238000003756 stirring Methods 0.000 abstract description 12
- 239000011267 electrode slurry Substances 0.000 abstract description 11
- 239000006185 dispersion Substances 0.000 abstract description 10
- 239000002002 slurry Substances 0.000 abstract description 10
- -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
- 239000011248 coating agent Substances 0.000 description 16
- 238000002156 mixing Methods 0.000 description 16
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- 238000005245 sintering Methods 0.000 description 15
- 229910003002 lithium salt Inorganic materials 0.000 description 13
- 159000000002 lithium salts Chemical class 0.000 description 13
- 239000000843 powder Substances 0.000 description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000005054 agglomeration Methods 0.000 description 6
- 230000002776 aggregation Effects 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000010902 jet-milling Methods 0.000 description 5
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- 238000004806 packaging method and process Methods 0.000 description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
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- 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
- 239000006258 conductive agent Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000009775 high-speed stirring Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
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- 239000000203 mixture Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
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- 239000003755 preservative agent Substances 0.000 description 3
- 230000002335 preservative effect Effects 0.000 description 3
- 239000000243 solution Substances 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
- 239000006256 anode slurry Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
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- 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
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- 229910052744 lithium Inorganic materials 0.000 description 2
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- 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
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- 230000015572 biosynthetic process Effects 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
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- 230000001276 controlling effect Effects 0.000 description 1
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- 239000011737 fluorine Substances 0.000 description 1
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- 238000010295 mobile communication Methods 0.000 description 1
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- 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 method for judging stability of the positive electrode material and application of the positive electrode material. The anode material is alpha-NaFeO2The structure is that the pH value of the anode 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 anode material is a 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 the advantages that the pH value difference value is within a certain range before and after ball milling, the stability is good, and the material has excellent processability and electricityChemical properties. According to the positive electrode material provided by the invention, local gel caused by dispersion processes such as stirring in the preparation process of the slurry can be avoided in the preparation process of the positive electrode slurry, the prepared positive electrode piece has lower diaphragm resistance, and the prepared battery has lower direct current impedance. The method for judging the stability of the cathode material provided by the invention has high accuracy, and the finally obtained result is extremely consistent with the stability matching degree of the cathode material.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a positive electrode material, a method for judging the stability of the positive electrode material and application of the positive electrode material.
Background
The lithium ion battery is a third generation small-sized storage battery following the nickel-cadmium battery and the nickel-hydrogen battery. As a novel chemical power supply, the self-energy-saving 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 of batteries required by portable electrical appliances and is beneficial to environmental protection, is widely applied to small electronic devices such as mobile communication, notebook computers, all-in-one machines and the like, and is also an ideal power supply used by future electric vehicles.
Having alpha-NaFeO2The ternary lithium nickel cobalt manganese and lithium nickel cobalt aluminum materials with the structure are one of the mainstream positive materials of the lithium ion power battery due to the higher gram capacity and the excellent dynamic performance.
The positive electrode material may be cracked or broken during the preparation of the electrode slurry due to the stirring dispersion process, and the cracking and breaking may occur among individual positive electrode material particles or between a plurality of different particles. The interface of the newly generated anode material after the cracks and the fracture is not passivated when exposed to a sintering atmosphere at high temperature, and does not have solid-phase reaction with the coating element or is wrapped by the coating element. Therefore, on one hand, a large number of dangling bonds are easily generated on the new interface, and protons are easily abstracted from the slurry; on the other hand, lithium ions are also easily separated from the lithium layer, and the acidity and alkalinity of the slurry are affected. Because the existing lithium ion battery anode mostly uses PVDF (polyvinylidene fluoride), which is easy to crosslink under the condition of overhigh pH, the anode material with excessive cracks or easy to dissociate is easy to generate local or whole gel near the cracks and broken areas in the slurry production process, so that the components are uneven, and uneven areas appear in the subsequent pole piece preparation, even the subsequent processing can not be carried out 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 products with better performance, lithium salt with stoichiometric ratio is often used in the sintering process in the production process, so as to ensure that the final product does not have the defects of low capacity, high impedance and the like caused by the lack of lithium ions. Excess lithium salt remains on the surface of the ternary material, rendering the material alkaline. When the positive electrode slurry is prepared, the residual alkali on the surface may react with the PVDF serving as the binder to cause local or even whole gel, so that the distribution of the positive electrode material, the binder and the conductive agent on the positive electrode sheet is uneven, and even the subsequent battery manufacturing process cannot be performed.
CN103392251A discloses a high-nickel cathode material with low soluble alkali content, which can control the residual lithium salt on the surface of the material to a certain extent by adjusting the manufacturing process, thereby achieving 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 process of the positive electrode slurry, in which the materials are always in the process of high-speed stirring, ball milling or mutual 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 a gel.
CN107732199A discloses a fluorine-containing lithium ion battery positive electrode material, which is coated by a liquid phase coating and evaporation drying method, and a coating agent is used to absorb residual alkali on the surface, but because the method is complicated and needs inert gas protection during evaporation drying, 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 wash solutions is therefore a simple and low cost method of surface modification. LiOH and Li on the surface of the high-nickel cathode material can be treated by a water washing process2CO3And the lithium in the internal crystal lattice of the material is dissolved into the aqueous solution after the material is washed, 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 cathode material, so that the structure of the cathode material is not easily damaged in the process of preparing the cathode slurry, and the electrochemical performance of the material is improved is a technical problem to be solved urgently.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a positive electrode material, a method for judging the stability of the positive electrode material and application of the positive electrode material. The positive electrode material provided by the invention has the advantages that the pH value difference value is within a certain range before and after ball milling, the stability is good, and the material has excellent processability and electrochemical performance. According to the positive electrode material provided by the invention, local gel caused by dispersion processes such as stirring in the preparation process of the slurry can be avoided in the preparation process of the positive electrode slurry, the prepared positive electrode piece has lower diaphragm resistance, and the prepared battery has lower direct current impedance. The method for judging the stability of the cathode material provided by the invention has high accuracy, and the finally obtained result is extremely consistent with the stability matching degree of the cathode material.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a positive electrode material, wherein the positive electrode material is alpha-NaFeO2The positive electrode material has a pH value m before ball milling, a pH value n after ball milling, and n-m is less than or equal to 0.15, wherein 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 cathode material is Lia(NixCoyM1-x-y)1-bM’bO2-cAcWherein a is more than or equal to 0.85 and less than or equal to 1.2, and x is more than or equal to 0.5<1, 0. ltoreq. y.ltoreq.0.2, 0. ltoreq. b.ltoreq.0.01, 0. ltoreq. c.ltoreq.0.2, M comprises Mn and/or Al, M' comprises any one or a combination of at least two of Al, Zr, Ti, Y, Sr, W or Mg, A comprises S, F or any one or a combination of at least two of N, for example, a may be 0.85, 0.9, 0.95, 1, 1.05, 1.1, 1.15 or 1.2 etc., x may be 0.5, 0.6, 0.7, 0.8, 0.9 or 1 etc., Y may be 0, 0.05, 0.1, 0.15 or 0.2 etc., 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., c may be 0, 0.02, 0.08, 0.15, 0.2, etc.
The positive electrode material provided by the invention has the advantages that the pH value difference value is less than or equal to 0.15 before and after ball milling, the stability is good, and the material has excellent processability and electrochemical performance. According to the positive electrode material provided by the invention, local gel caused by dispersion processes such as stirring in the preparation process of the slurry can be avoided in the preparation process of the positive electrode slurry, the prepared positive electrode piece has lower diaphragm resistance, and the prepared battery has lower direct current impedance.
In the invention, the dispersion process of the material can be simulated by ball milling, and the occurrence conditions of cracks and breakage in the process can be investigated by the pH value difference before and after ball milling, so that the pH value difference can well reflect the stability of the material.
Preferably, n-m.ltoreq.0.1, such as 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, or 0.1, etc.
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 soft agglomerates which can be broken are less. The ternary cathode 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, such as 45min, 46min, 47min, 48min, 49min, 50min, 51min, 52min, 53min, 54min, 55min, 56min, 57min, 58min, 59min or 60 min.
In the invention, if the ball milling time is too short, the crystal particles agglomerated together cannot be thoroughly crushed, and the effect of detecting the agglomeration degree of the particles cannot be achieved. If the ball milling time is too long, the single crystal particles may be cracked and broken, and the determination result may be misled.
Preferably, in the ball milling, the acceleration of the ball milling is 65-75 m/s2E.g. 65m/s2、66m/s2、67m/s2、68m/s2、69m/s2、70m/s2、71m/s2、72m/s2、73m/s2、74m/s2Or 75m/s2And the like.
In the invention, if the acceleration in the ball milling process is too small, the crystal particles agglomerated together cannot be thoroughly crushed, and the effect of detecting the agglomeration degree of the particles cannot be achieved. And the single crystal particles are broken due to overlarge acceleration, and the judgment result is misled.
Preferably, in the ball milling, the volume mass ratio of the ball milling beads to the positive electrode material is 200-250 mm3In g, e.g. 200mm3/g、205mm3/g、210mm3/g、215mm3/g、220mm3/g、225mm3/g、230mm3/g、235mm3/g、240mm3/g、245mm3G or 250mm3And/g, etc.
In the invention, the volume of the ball milling beads refers to the sum of the volumes of all the beads during ball milling. When the volume-mass ratio of the ball-milling beads to the positive electrode material is too small, the agglomerated crystal particles cannot be thoroughly crushed, and the effect of detecting the agglomeration degree of the particles cannot be achieved. Too large mass ratio may cause the single crystal particles to be broken, and mislead the judgment result.
Preferably, the cathode material is a single crystal cathode material and/or a single crystal-like cathode material.
Preferably, the D50 of the positive electrode material is 2-4 μm, such as 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.
The median particle size of the cathode material provided by the invention is within the range of 1.5-4 mu m, and the cathode material can give consideration to gram-volume exertion, direct current impedance and electrochemical stability. The excessively large median diameter causes an excessively long diffusion path of lithium ions in the particles, and influences the gram volume performance and the impedance of the material; an excessively small median particle diameter leads to a low stability of the material.
In a second aspect, the present invention provides a method for determining the stability of the positive electrode material according to the first aspect, the method comprising:
and ball-milling the anode material to obtain a pH value m before ball milling, taking a pH value n after ball milling and a difference value of n-m as a judgment condition, and judging the stability of the anode material.
The ball milling provided by the invention is carried out by adopting planetary ball milling equipment, and comprises double planetary ball milling and the like.
In the invention, when the pH value difference (n-m) before and after ball milling is less than or equal to 0.15, the stability of the anode material is judged to be good, and when the pH value difference (n-m) is more than 0.15, the stability of the material is poor, so that the processing performance of the material in anode slurry and an anode pole piece is influenced, and further the electrochemical performance of the battery is influenced.
The anode material can be regulated and controlled in the preparation method according to the judgment method provided by the invention, for example, the sintering temperature, the element doping or coating amount, or the crushing condition and the like in the preparation process can be regulated and controlled through the pH value difference of the obtained anode material, so that the stability of the material can be improved, and the single crystal or single crystal-like particles of the material can be more completely grown, namely the judgment method provided by the invention provides a good auxiliary effect for the preparation of the anode material, and the anode material with good stability and excellent electrochemical performance can be obtained through the judgment method provided by the invention.
According to the method, the occurrence conditions of cracking and crushing 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, the method for judging the stability of the anode material provided by the invention has high accuracy, and the finally obtained result is extremely consistent with the stability matching degree of the anode material.
Preferably, the ball milling time is 45-60 min, such as 45min, 46min, 47min, 48min, 49min, 50min, 51min, 52min, 53min, 54min, 55min, 56min, 57min, 58min, 59min or 60 min.
In the invention, if the ball milling time is too short, the agglomerated crystal particles cannot be thoroughly crushed, and 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 may be cracked and crushed, and the judgment result is misled.
Preferably, in the ball milling, the acceleration of the ball milling is 65-75 m/s2E.g. 65m/s2、66m/s2、67m/s2、68m/s2、69m/s2、70m/s2、71m/s2、72m/s2、73m/s2、74m/s2Or 75m/s2And the like.
In the invention, when the acceleration in the ball milling process is too small, the crystal particles agglomerated together cannot be thoroughly crushed, the effect of detecting the agglomeration degree of the particles cannot be achieved, and when the acceleration is too large, the single crystal particles can be cracked and crushed, and the judgment result can be misled.
Preferably, the acceleration of the ball mill is calculated by the formula 4 x pi2*r*f2And/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 to the positive electrode material is 200-250 mm3In g, e.g. 200mm3/g、205mm3/g、210mm3/g、215mm3/g、220mm3/g、225mm3/g、230mm3/g、235mm3/g、240mm3/g、245mm3G or 250mm3And/g, etc.
Preferably, the volume mass ratio of the ball milling beads to the positive electrode material is calculated by 4/3 pi r1 3*n/m，r1The radius of the ball milling beads is shown, n is the number of the ball milling beads, and m is the mass of the anode material.
In the invention, the volume of the ball milling beads refers to the sum of the volumes of all the beads during ball milling. If the volume-mass ratio of the ball-milling beads to the positive electrode material is too low, the crystal particles agglomerated together 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 preferred embodiment, the determination method includes:
the anode material is heated at 65-75 m/s2Performing ball milling for 45-60 min at the accelerated speed to obtain a pH value m before ball milling, taking the pH value n after ball milling and the difference between n and m as a judgment condition, and judging the stability of the anode material;
wherein the acceleration of the ball millIs calculated by the formula g-4 pi2*r*f23600, 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 beads to positive electrode material is 200-250 mm3/g。
In a third aspect, the present invention also provides a lithium ion battery, which includes the positive electrode material according to the first aspect.
Illustratively, the present invention provides a preparation method of the cathode material, the preparation method comprising:
mixing NixCoyM1-x-y(OH)2And mixing the precursor with lithium salt (doping or coating can be carried out), then carrying out heating sintering, carrying out jaw crushing and air flow crushing after sintering, and obtaining the cathode material.
NixCoyM1-x-y(OH)2The selection of the particle size and specific surface area of the precursor is not particularly required, but in order to obtain a good single crystal or single-crystal-like morphology, the particle size is recommended to satisfy the volume distribution 50% integrated value Dv50 of 2-7 μm and the specific surface area of 5-15 m2Per gram of small particle precursor.
Lithium carbonate or lithium hydroxide can be used as the lithium salt, and the molar ratio of the lithium salt to the precursor can be set to be 0.95-1.1.
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 non-oxygen elements corresponding to the oxide to the precursor is recommended to be 50-10000 ppm.
The mixing equipment used in the process of mixing the precursor and the lithium salt can be a high-speed mixer or a colter mixer, and the mixing requires that the difference of all the mixed substances is less than 3 percent when 4 times of random sampling is carried out to compare the mass percentage of each element.
The equipment used for temperature rise sintering needs to realize the functions of temperature control and gas flow control. The form of the furnace can be a box furnace or a roller kiln, and the roller kiln is generally recommended to be used. And (3) filling the mixed precursor, lithium salt and doping coating agent into a sagger, and feeding into a furnace body to finish sintering.
The temperature rise rate during sintering is not particularly required. In order to uniformly and jointly heat the precursor, 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 temperature rising stage to help discharge gas products such as water, carbon dioxide and the like generated by the reaction.
The constant temperature used during sintering depends on the proportion of the materials and the performance requirements of the materials. For the material with x being more than or equal to 0.5 and less than 0.75, the constant temperature is recommended to be selected within the range of 900-1200 ℃; for the material with 0.75< x <1, the constant temperature is recommended to be selected within the range of 750-1050 ℃. The time of constant-temperature sintering is recommended to be 4-12 hours, and air or oxygen can be introduced into the furnace body in the constant-temperature stage to help discharge gas products such as water, carbon dioxide and the like generated by the reaction.
And crushing the sintered material block by using an air flow mill or a disc mill after jaw crushing. The air pressure of the jet mill and the frequency of the grading wheel are adjusted, so that the crushing and the particle size control of the sintered material are realized. The recommended air pressure selection range is 0.2-0.9 MPa, and the frequency of the grading wheel 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 classification wheel should be reduced; if the suitable particle size is smaller than the resulting particle size, the air pressure used in the air-jet mill or the frequency of the classifier wheel should be increased. The suitable particle size and crushing degree of the corresponding sintered material can be judged by the following ball milling method in the patent.
The ternary cathode material with more excellent performance can be sintered for multiple times. Taking the second sintering as an example, the product obtained by the first sintering and crushing can be mixed with a doping or coating agent, and then the mixture is kept at a constant temperature of 500-1000 ℃ for 3-10 hours. The heating rate and the specific conditions of gas introduction are the same as those of the first sintering. Before the secondary sintering, a proper amount of lithium salt (the molar ratio of the lithium salt to the primary sintered product is recommended to be controlled to be 0.5-1%) can be added and mixed together. After sintering, direct packaging or one-time airflow crushing can be selected according to material properties, and the anode material disclosed by the patent is obtained by adjusting 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 the advantages that the pH value difference value is within a certain range before and after ball milling, the stability is good, and the material has excellent processability and electrochemical performance. According to the positive electrode material provided by the invention, local gel caused by dispersion processes such as stirring in the preparation process of the slurry can be avoided in the preparation process of the positive electrode slurry, the prepared positive electrode piece has lower diaphragm resistance, and the prepared battery has lower direct current impedance. According to the battery provided by the invention, the diaphragm resistance of the positive pole piece is as low as 769m omega, the DCR of the battery cell is as low as 8.7 omega, the ball milling time is regulated and controlled within 45-60 min, the diaphragm resistance of the positive pole piece is as low as 541m omega, and the DCR of the battery cell is as low as 6.5 omega. The method for judging the stability of the cathode material provided by the invention has high accuracy, and the finally obtained result is extremely consistent with the stability matching degree of the cathode material.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
In one embodiment, the present invention provides a method for determining stability of a positive electrode material, the method comprising:
the anode material is heated at 65-75 m/s2Performing ball milling for 45-60 min at the accelerated speed to obtain a pH value m before ball milling, taking the pH value n after ball milling and the difference between n and m as a judgment condition, and judging the stability of the anode material;
wherein the calculation formula of the acceleration of the ball mill is g-4 pi2*r*f23600, 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 beads to positive electrode material is 200-250 mm3/g。
Example 1
This example provides a positive electrode material (D50 is 2 μm) whose chemical formula is shown in table 1, and the difference n-m is shown in table 1 after the determination method of the above embodiment.
The ball milling conditions are as follows:
in this example, PM100 equipment from Leichi company was selected, and 9 zirconia beads with a diameter of 10mm and 20g of positive electrode material were added into a material tank, that is, the volume-to-mass ratio of the beads to the positive electrode material was 235.5mm3Per g, run at 300rpm for 60 min. The diameter of the sun gear of the device is 0.141m, and the acceleration g of ball milling calculated to be 69.5m/s2。
The preparation method of the cathode material provided in this embodiment is as follows:
selecting Ni0.6Co0.1M0.3(OH)2Precursor, Dv50 ═ 3.5 μm, specific surface area 9m2(ii) in terms of/g. Mixing with lithium carbonate at a molar ratio of 1:1.05, and adding 0.12 wt% (based on the precursor) of nano-sized ZrO2The powders are mixed uniformly in a high-speed mixer. After loading into a sagger, the temperature is raised to 930 ℃ at a heating rate of 5 ℃/min and kept for 8 hours. After the material block is cooled, the material block is crushed in an air flow mill through a jaw crusher. The jet milling parameters were set to 0.7MPa air pressure and 40rpm classifier frequency. The Dv50 of the material after the end of the comminution was 2 μm. Mixing the material with 0.15 wt% of nano Al2O3The powder was mixed uniformly using a high speed mixer, charged into a sagger and then heated to 550 ℃ at a heating rate of 10 ℃/min and held for 5 hours. And (4) directly packaging the cooled powder without airflow crushing to obtain the finished product cathode material.
Example 2
This example provides a positive electrode material (D50 is 3.2 μm) whose difference in n-m is shown in table 1 and whose chemical formula is also shown in table 1 after the determination method of the above embodiment.
The ball milling conditions are as follows:
in this example, PM100 equipment from Leichi company was selected, 10 zirconia beads with a diameter of 10mm and 21g of a positive electrode material were added into a material tank, that is, the volume-to-mass ratio of the beads to the positive electrode material was 250mm3Per g, run at 350rpm for 45 min. The diameter of the sun gear of the device is 0.141m, and the acceleration of ball milling can be obtained by calculationg is 69.5m/s2。
The preparation method of the cathode material provided in this embodiment is as follows:
selecting Ni0.6Co0.1M0.3(OH)2Precursor, Dv50 ═ 3.5 μm, specific surface area 9m2(ii) in terms of/g. Mixing with lithium carbonate at a molar ratio of 1:1.05, and adding 0.12 wt% (based on the precursor) of nano-sized ZrO2The powders are mixed uniformly in a high-speed mixer. After loading into a sagger, the temperature is raised to 940 ℃ at the heating rate of 5 ℃/min and kept for 8 hours. After the material block is cooled, the material block is crushed in an air flow mill through a jaw crusher. The jet milling parameters were set to 0.5MPa air pressure and 35rpm classifier frequency. The Dv50 of the material after the end of the comminution was 3.2 μm. Mixing the material with 0.15 wt% of nano Al2O3The powder was mixed uniformly using a high speed mixer, charged into a sagger and then heated to 550 ℃ at a heating rate of 10 ℃/min and held for 5 hours. And (4) directly packaging the cooled powder without airflow crushing to obtain the finished product cathode material.
Example 3
This example provides a positive electrode material (D50 is 4 μm) whose chemical formula is shown in table 1, and the difference n-m is shown in table 1 after the determination method of the above embodiment.
The ball milling conditions are as follows:
in this example, PM100 equipment from Leichi company was selected, 8 zirconia beads with a diameter of 10mm and 20.5g of positive electrode material were added into a material tank, that is, the volume-to-mass ratio of the beads to the positive electrode material was 204.3mm3The/g was run at 300rpm for 50 min. The diameter of the sun gear of the device is 0.141m, and the acceleration g of ball milling calculated to be 69.5m/s2。
The preparation method of the cathode material provided in this embodiment is as follows:
selecting Ni0.6Co0.1M0.3(OH)2Precursor, Dv50 ═ 3.5 μm, specific surface area 9m2(ii) in terms of/g. Mixing with lithium carbonate at a molar ratio of 1:1.05, and adding 0.12 wt% (based on the precursor) of nano-sized ZrO2The powders are mixed uniformly in a high-speed mixer. Placing into a sagger, heating to 980 deg.C at a heating rate of 5 deg.C/minAnd held for 8 hours. After the material block is cooled, the material block is crushed in an air flow mill through a jaw crusher. The jet milling parameters were set to 0.4MPa of air pressure and 30rpm of the classifier wheel. The Dv50 of the material after the end of the comminution was 3.2 μm. Mixing the material with 0.15 wt% of nano Al2O3The powder was mixed uniformly using a high speed mixer, charged into a sagger and then heated to 550 ℃ at a heating rate of 10 ℃/min and held for 5 hours. And (4) directly packaging the cooled powder without airflow crushing to obtain the finished product cathode material.
Example 4
The difference between this example and comparative example 1 is that the ball milling time in this example was 30 min.
The conditions and methods for the preparation of the remaining materials were kept 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 is 75 min.
The conditions and methods for the preparation of the remaining materials remained the same as in example 1.
Comparative example 1
The comparative example differs from example 1 in that the positive electrode material in the comparative example has a pH n-m of 0.2.
The ball milling conditions and methods were consistent with example 1.
The preparation method of the cathode material provided in this embodiment is as follows:
selecting Ni0.6Co0.1M0.3(OH)2Precursor, Dv50 ═ 3.5 μm, specific surface area 9m2(ii) in terms of/g. Mixing with lithium carbonate at a molar ratio of 1:1.05, and adding 0.12 wt% (based on the precursor) of nano-sized ZrO2The powders are mixed uniformly in a high-speed mixer. After loading into a sagger, the temperature is raised to 930 ℃ at a heating rate of 5 ℃/min and kept for 8 hours. After the material block is cooled, the material block is crushed in an air flow mill through a jaw crusher. The jet milling parameters were set to 0.4MPa of air pressure and 30rpm of the classifier wheel. The Dv50 of the material after the end of the comminution was 3.6 μm. Mixing the material with 0.15 wt% of nano Al2O3The powder was mixed uniformly using a high speed mixer, charged into a sagger and then heated to 550 ℃ at a heating rate of 10 ℃/min and held for 5 hours. Cooled powderAnd directly packaging the powder without jet milling to obtain the finished product of the cathode material.
Mixing the positive electrode materials provided in examples 1-5 and comparative example 1 with conductive agent carbon black and binder PVDF according to a ratio of 97:1.7:1.3, adding the mixture into an organic solvent NMP, and stirring at a high speed to form a uniform dispersion liquid; and after the high-speed stirring is finished, defoaming in a stirring tank under negative pressure to obtain the anode slurry suitable for coating. 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 piece with the required shape. The compaction density of the coating area of the positive active material is controlled to be 3.4g/cm in the cold pressing process3Within.
Mixing the negative active material with conductive agent carbon black, binder and CMC according to the ratio of 96.8:1.2:1.2:0.8, adding the mixture into deionized water, and stirring at high speed to form uniform dispersion liquid; and after the high-speed stirring is finished, defoaming in a stirring tank under negative pressure to obtain the negative electrode slurry suitable for coating. Coating the obtained negative electrode slurry on a copper foil through a transfer coater, and drying, cold pressing and slitting to prepare the negative electrode piece with the required shape. The compacted density of a coating area of the negative active material is controlled to be 1.6g/cm in the cold pressing process3Within.
And placing the positive and negative pole pieces on two sides of the isolating film and winding to form a roll core, and keeping the uncoated area to be connected with the nickel pole lug through ultrasonic welding. And the roll core is wrapped by an aluminum plastic film and then is subjected to heat sealing, and one side of the roll core is reserved for injecting liquid.
Adding 13 wt% of LiPF into a mixed solvent of EC EMC DEC 3:5:26And 1 wt% of vinylene carbonate and 2 wt% of DTD are used as lithium salt and additives to prepare electrolyte, and the electrolyte is injected into the aluminum plastic film wrapped with the winding core. And then carrying out vacuum packaging, standing and formation to obtain the lithium ion battery.
The cells provided in examples 1-5 and comparative example 1 were tested under the following conditions:
and (3) pH test: the measurement was carried out using a pH meter which was calibrated for future use, and then 5g of a single sample was accurately weighed and placed in a 100ml beaker. Adding 45g of deionized water, placing the magnetic rotor into a beaker, sealing the whole preservative film to isolate air, and placing the beaker on a magnetic stirrer to stir for 30 min. The temperature was kept at 25 ℃ throughout. And after stirring is finished, the supernatant is not required to be taken out, the probe of the pH meter is cleaned and then wiped dry, the probe penetrates through the preservative film and is inserted into the supernatant of the solution, and the beaker is sealed by the preservative film to isolate air for testing to obtain the pH value. The test was repeated three times and the average was taken.
Testing the resistance of the diaphragm: the energy-efficient BER2500 is used, the pressure is set to be 25kg, and the dwell time is 400 s. And (3) placing the coated and dried pole piece between two probes of equipment, and using the equipment with software to operate and measure to obtain the conductivity of the pole piece.
DCR test: the SOC state of the battery was adjusted to 50% (i.e., the battery was charged from a fully discharged state to 50% of the rated capacity) at a rate of 0.33C (i.e., 0.33 times the ampere-hour of the rated capacity of the battery was set as the current magnitude) using a charge and discharge device, the battery was subjected to a discharge operation at a constant current a of 3C after 30 minutes of standing, and the voltage change Δ V during the discharge was recorded, and DCR was Δ V/a.
The chemical formulas of the positive electrode materials in examples 1 to 5 and comparative example 1, the pH before (i.e., initial) ball milling, the ball milling time, the pH after ball milling, the n-m value, the sheet resistance of the positive electrode sheet, and the DCR of the cell are shown in table 1, respectively.
TABLE 1
From the data results of example 1 and example 4, it is known that if the ball milling time is too short, a large amount of unopened soft aggregates remain in the material, and even if the pH difference is small, the defect of poor stability of the material cannot be reflected.
From the data results of example 1 and example 5, it is known that excessively long ball milling time may cause cracks and damages to the complete single crystal particles of the material, which may result in large pH change and misjudgment on the stability of the material.
From the data results of the example 1 and the comparative example 1, it can be seen that the positive electrode material has an excessively large difference n-m before and after ball milling, which indicates that the stability of the material is poor, and the sheet resistance of the electrode sheet prepared by the same method is significantly increased, and the DCR of the battery is relatively high.
In conclusion, the positive electrode material provided by the invention has the advantages that the pH value difference value is within a certain range before and after ball milling, the stability is good, and the material has excellent processability and electrochemical performance. According to the positive electrode material provided by the invention, local gel caused by dispersion processes such as stirring in the preparation process of the slurry can be avoided in the preparation process of the positive electrode slurry, the prepared positive electrode piece has lower diaphragm resistance, and the prepared battery has lower direct current impedance. According to the battery provided by the invention, the diaphragm resistance of the positive pole piece is as low as 769m omega, the DCR of the battery cell is as low as 8.7 omega, the ball milling time is regulated and controlled within 45-60 min, the diaphragm resistance of the positive pole piece is as low as 541m omega, and the DCR of the battery cell is as low as 6.5 omega. The method for judging the stability of the cathode material provided by the invention has high accuracy, and the finally obtained result is extremely consistent with the stability matching degree of the cathode material.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The cathode material is characterized by being alpha-NaFeO2The structure is that the pH value of the anode material before ball milling is m, the pH value after ball milling is n, and n-m is less than or equal to 0.15;
the chemical general formula of the cathode material is Lia(NixCoyM1-x-y)1-bM’bO2-cAcWherein a is more than or equal to 0.85 and less than or equal to 1.2, and x is more than or equal to 0.5<1, y is more than or equal to 0 and less than or equal to 0.2, b is more than or equal to 0 and less than or equal to 0.01, c is more than or equal to 0 and less than or equal to 0.2, M comprises Mn and/or Al,m' comprises any one or combination of at least two of Al, Zr, Ti, Y, Sr, W or Mg, and A comprises any one or combination of at least two of S, F or N.
2. The positive electrode material as claimed in claim 1, wherein n-m is 0.1 or less.
3. The positive electrode material according to claim 1 or 2, wherein the ball milling time is 45 to 60 min.
4. The positive electrode material as claimed in any one of claims 1 to 3, wherein the acceleration of ball milling is 65 to 75m/s in the ball milling2。
5. The positive electrode material as claimed in any one of claims 1 to 4, wherein the volume mass ratio of the ball milling beads to the positive electrode material in the ball milling is 200 to 250mm3/g。
6. The cathode material according to any one of claims 1 to 5, wherein the cathode material is a single crystal cathode material and/or a single crystal-like cathode material;
preferably, D50 of the cathode material is 2-4 μm.
7. A method for determining the stability of a positive electrode material according to any one of claims 1 to 6, characterized in that the method for determining comprises:
and ball-milling the anode material to obtain a pH value m before ball milling, taking a pH value n after ball milling and a difference value of n-m as a judgment condition, and judging the stability of the anode material.
8. The method for determining the stability of a positive electrode material according to claim 7, wherein the ball milling time is 45 to 60 min;
preferably, in the ball milling, the acceleration of the ball milling is 65-75 m/s2；
Preferably, the acceleration of the ball mill is calculated by the formula 4 x pi2*r*f23600, 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 to the positive electrode material is 200-250 mm3/g。
9. The method for determining the stability of the positive electrode material according to claim 7 or 8, characterized by comprising:
the anode material is heated at 65-75 m/s2Performing ball milling for 45-60 min at the accelerated speed to obtain a pH value m before ball milling, taking the pH value n after ball milling and the difference between n and m as a judgment condition, and judging the stability of the anode material;
wherein the calculation formula of the acceleration of the ball mill is 4 x pi2*r*f23600, 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 beads to positive electrode material is 200-250 mm3/g。
10. A lithium ion battery comprising the positive electrode material according to any one of claims 1 to 6.
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| CN111129448A (en) * | 2019-11-20 | 2020-05-08 | 浙江美都海创锂电科技有限公司 | Single crystal type nickel cobalt lithium manganate ternary cathode material and low-temperature sintering preparation method thereof |
| CN111900380A (en) * | 2020-08-10 | 2020-11-06 | 湖北融通高科先进材料有限公司 | Method for preparing nickel cobalt lithium manganate single crystal ternary material |
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| CN114927691A (en) * | 2022-05-20 | 2022-08-19 | 上海瑞浦青创新能源有限公司 | Ternary positive electrode slurry, preparation method and application in lithium ion battery |
| CN116609367A (en) * | 2023-07-19 | 2023-08-18 | 天津力神电池股份有限公司 | Selection method and application of target silicon anode material |
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