CN118825256A - Positive electrode material, battery comprising same and power utilization device - Google Patents
Positive electrode material, battery comprising same and power utilization device Download PDFInfo
- Publication number
- CN118825256A CN118825256A CN202310366399.4A CN202310366399A CN118825256A CN 118825256 A CN118825256 A CN 118825256A CN 202310366399 A CN202310366399 A CN 202310366399A CN 118825256 A CN118825256 A CN 118825256A
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- Prior art keywords
- positive electrode
- electrode material
- lithium
- battery
- lithium ion
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 105
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 77
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 67
- 150000002500 ions Chemical class 0.000 claims abstract description 33
- 150000001768 cations Chemical class 0.000 claims abstract description 15
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 6
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 6
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 229910052700 potassium Inorganic materials 0.000 claims description 15
- 239000007773 negative electrode material Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 229910052723 transition metal Inorganic materials 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 1
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- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 150000004804 polysaccharides Chemical class 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical compound [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 229940082509 xanthan gum Drugs 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The application relates to a multi-cation positive electrode material, which has a general formula of Li aLxNibCocMndM(1‑b‑c‑d)OeNf or mLi2MnO3·(1-m)LiaLxNibCocMndM(1‑b‑c‑d)OeNf,, wherein L ions are cations with a radius larger than that of Li ions, M comprises at least one of Mg, zr, al, B, ta, mo, W, nb, sb, la, N comprises at least one of F, S and P, 0 < a < 1,0 < b < 1,0 < c < 1,0 < d < 1,0 < b+c+d < 1,0 < e < 2,0 < f < 2,0 < M < 1,0 < x < 0.8, a+x=1, e+f=2, and the following relational expression is satisfied: 2.5 x 10 ‑6≤x/v≤2.5×10‑3, wherein v is the gram capacity of the polycationic positive electrode material. The application also relates to a lithium ion battery containing the positive electrode material and an electric device containing the lithium ion battery.
Description
Technical Field
The application relates to the technical field of batteries, in particular to a positive electrode material, a battery containing the positive electrode material and an electric device.
Background
Lithium ion batteries are widely used in the fields of pure electric vehicles, hybrid electric vehicles, smart grids and the like. Along with the large-scale application of the lithium ion battery, the field also provides higher requirements on energy density, multiplying power performance, safety performance and the like. With the increasing demand of lithium ion energy density, layered cathode materials are gradually developed from the earliest low-nickel materials to the current high-gram-capacity materials such as high-nickel and lithium-rich manganese-based materials. However, due to factors such as lithium-nickel mixed arrangement, the high-nickel and lithium-rich manganese-based materials are poor in structural stability, and the cycle performance of the battery cell is seriously affected.
Accordingly, there remains a need in the art to develop a new active material for a positive electrode that has improved stability to inhibit lithium nickel miscibility and has a high gram capacity and good cycle performance.
Disclosure of Invention
The present application has been made in view of the above problems, and an object of the present application is to provide a positive electrode active material that can effectively suppress lithium nickel mixed discharge with improved stability at a high gram capacity, thereby solving the technical problem that the poor stability of the positive electrode material in the prior art adversely affects the cell cycle performance.
In order to achieve the above object, the first aspect of the present application provides a multi-cation positive electrode material, wherein the positive electrode material has a general formula of Li aLxNibCocMndM(1-b-c-d)OeNf or mLi2MnO3·(1-m)LiaLxNibCocMndM(1-b-c-d)OeNf,, wherein L ions are cations having a radius larger than that of Li ions, M includes at least one of Mg, zr, al, B, ta, mo, W, nb, sb, la, N includes at least one of F, S and P, 0 < a < 1,0 < b < 1,0 < c < 1,0 < d < 1,0 < b+c+d < 1,0 < e < 2,0 < f < 2,0 < M < 1,0 < x < 0.8, a+x=1, e+f=2,
And satisfies the following relationship:
2.5 x 10 -6≤x/v≤2.5×10-3, wherein v is the gram capacity of the polycationic positive electrode material.
By replacing part of lithium of the layered anode material with cations with larger ionic radius, the layered structure is supported, lithium-nickel mixed discharge is inhibited, and the stability of the material is improved. In addition, by setting the ratio of the molar amount of the cations having a larger ion radius to be doped to the gram capacity of the positive electrode material, the cycle life of the lithium ion battery including the positive electrode material can be effectively adjusted.
In any embodiment, 0.001 < x.ltoreq.0.5, preferably 0.003 < x.ltoreq.0.05. In any embodiment, in the multi-cation positive electrode material, x and v satisfy the following formula: 2.5X10 -5≤x/v≤2.5×10-4. By further adjusting the ratio of x/v, the stability of the positive electrode material can be further improved.
In any embodiment, the gram capacity v of the multi-cation positive electrode material meets 120 mAh/g.ltoreq.v.ltoreq.300 mAh/g.
In any embodiment, the element of the L ion includes at least one of an alkali metal element, an alkaline earth metal element, a transition metal element, and other metal elements of the main group other than lithium element. In a further embodiment, the alkali metal element comprises at least one of Na, K, rb, cs; the alkaline earth metal element comprises at least one of Mg, ca and Sr; the transition metal element includes Y; and the main group other metal element includes Bi. In a further embodiment, the elements of the L ion comprise at least two of Na, K, rb, cs; optionally, the molar ratio of each of the at least two elements is greater than 0.5% based on the molar amount of Li ions.
In any embodiment, in the multi-cation positive electrode material, a satisfies 0.5.ltoreq.a < 1; optionally, 0.8.ltoreq.a < 1.
In any embodiment, in the multi-cation positive electrode material, 0.05.ltoreq.b.ltoreq.0.98, and 0.05.ltoreq.c.ltoreq.0.85.
A second aspect of the application provides a lithium ion battery comprising a positive electrode, wherein the positive electrode comprises a positive electrode material according to the first aspect of the application.
In any embodiment, the lithium ion battery comprises a negative electrode, the negative electrode active material of the negative electrode comprising at least one of graphite, hard carbon, and soft carbon.
A third aspect of the application provides an electrical device comprising a lithium ion battery according to the second aspect of the application.
Drawings
In order to more clearly illustrate the technical solution of the present application, the following will briefly describe the drawings that are required to be used in the embodiments of the present application. It is apparent that the drawings described below are only some embodiments of the present application and that other drawings may be obtained from the drawings without inventive work for those of ordinary skill in the art.
Fig. 1 is a schematic view of a lithium ion secondary battery in an embodiment of the application.
Fig. 2 is an exploded view of the lithium ion secondary battery in one embodiment of the present application shown in fig. 1.
Fig. 3 is a schematic view of a battery pack in one embodiment of the present application.
Fig. 4 is an exploded view of the battery pack in one embodiment of the present application shown in fig. 3.
Fig. 5 is a schematic view of an apparatus in which a battery pack is used as a power source in one embodiment of the present application.
Description of the reference numerals
1. Battery pack
2. Upper box body
3. Lower box body
4. Battery module
5. Lithium ion secondary battery
51. Shell body
52. Electrode assembly
53. Cover plate
Detailed Description
For simplicity, the present application specifically discloses some numerical ranges. However, any lower limit may be combined with any upper limit to form a range not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and any upper limit may be combined with any other upper limit to form a range not explicitly recited. Furthermore, each separately disclosed point or individual value may itself be combined as a lower limit or upper limit with any other point or individual value or with other lower limit or upper limit to form a range not explicitly recited.
With the increasing demand of lithium ion energy density, layered cathode materials gradually develop from the earliest low-nickel materials to the high-gram-capacity materials such as high-nickel and lithium-rich manganese-based materials. However, due to factors such as lithium-nickel mixed arrangement, the high-nickel and lithium-rich manganese-based materials are poor in structural stability, and the cycle performance of the battery cell is seriously affected. For example, during charging, the low-valence nickel in the transition metal layer migrates to occupy the vacancies of lithium ions, resulting in the destruction of the structure of the high-gram-capacity cathode material and deterioration of its stability and safety properties.
The inventor finds that by doping a certain amount of cations with the radius larger than that of Li ions in the positive electrode material for the lithium ion battery to replace part of lithium ions, the doped cations can play a role in supporting a layered structure due to the fact that the ionic radius is larger than that of lithium, so that lithium-nickel mixed discharge is inhibited, and the stability of the material is improved. However, the doping amount of the cations and the gram-volume of the positive electrode material must satisfy a certain relationship to satisfy the stabilization effect of the doping element.
Specifically, the first aspect of the application provides a multi-cation positive electrode material, which has a general formula of Li aLxNibCocMndM(1-b-c-d)OeNf or mLi2MnO3·(1-m)LiaLxNibCocMndM(1-b-c-d)OeNf,, wherein L ions are cations with a radius larger than that of Li ions, M comprises at least one of Mg, zr, al, B, ta, mo, W, nb, sb, la, N comprises at least one of F, S and P, 0< a < 1, 0< b < 1, 0< c < 1, 0< d < 1, 0< b+c+d < 1, 0< e < 2, 0< f < 2, 0< M < 1, 0< x < 0.8, a+x=1, e+f=2,
And satisfies the following relationship:
2.5 x 10 -6≤x/v≤2.5×10-3, wherein v is the gram capacity of the polycationic positive electrode material.
Without being bound by any particular theory, the inventors believe that the larger ionic radius of these elements to some extent impedes the occupation of lithium ion vacancies by the positive electrode material by partial substitution of lithium ions by cations L having ionic radii greater than the Li ionic radius, preventing the layered structure of the positive electrode material from being transformed into a spinel structure, thereby contributing to an improvement in the stability of the layered structure. In addition, the larger ionic radius of these cations also increases the ion diffusion path, helping to improve the rate capability of the material. However, the doping amounts of these elements need to be controlled within a certain range, and in particular, too small doping amounts are insufficient to achieve the supporting effect with respect to the gram capacity of the positive electrode material, and too large doping amounts may rather hinder ion transport and reduce the gram capacity. For example, for the multi-cation positive electrode material meeting the relation of 2.5 multiplied by 10 -6≤x/v≤2.5×10-3, on one hand, elements such as sodium ions or potassium ions and the like with larger radius than lithium in the novel positive electrode material can play a supporting role on lithium positions, enhance the mixed discharge energy barrier, prevent the Li/Ni mixed discharge of the layered cathode from being aggravated, and improve the stability of the layered structure so as to further improve the cycle performance. The multi-cation positive electrode material can be embedded into a negative electrode material as well, wherein ions with larger ionic radius play a supporting role in graphite, so that the expansion/contraction of graphite caused by ions with smaller ionic radius in the embedding/extracting process is reduced, the stability of SEI film is improved, and the consumption of active lithium is reduced. When the x/v of the positive electrode material is less than 2.5 multiplied by 10 -6, the doped ions are insufficient in quantity, the supporting effect cannot be achieved, and the improvement effect is not obvious. When x/v in the positive electrode material is more than 2.5×10 -3, a large amount of doped ions with larger radius can obstruct the transmission of lithium ions, so that the side reaction between the electrolyte and the interface is aggravated, the impedance is increased, the gram capacity of the material is reduced, and the service life is also difficult to realize. The gram capacity of the positive electrode material can be measured by the following method: the button cell was fabricated, charged at constant voltage after constant current at 0.1C, discharged at 0.1C, and the capacity was measured, divided by the mass of active material to obtain gram capacity. In the present invention, the gram capacity of the positive electrode material refers to the gram capacity measured at 25 ℃, unless otherwise specified.
In some embodiments, in the multi-cation positive electrode material, x satisfies 0.001 < x.ltoreq.0.5, alternatively 0.003 < x.ltoreq.0.05. x represents the doping ratio of the cation L with the ionic radius larger than that of Li ions in Li ions. The stabilizing effect of the positive electrode material by the cations L can be further improved by adjusting the positive electrode material.
In some embodiments, in the multi-cation positive electrode material, x and v satisfy the following formula: 2.5X10 -5≤x/v≤2.5×10-4. As described above, the ratio of the doping amount of the positive ion L to the gram capacity of the positive electrode material needs to be controlled within a certain range, and can be further adjusted to achieve further improvement of the stabilizing effect of the positive electrode material. In a further selected ratio range, the cycle life of a lithium ion battery comprising the positive electrode material is improved more significantly.
In some embodiments, the gram capacity v of the multi-cation positive electrode material satisfies 120 mAh/g.ltoreq.v.ltoreq.300 mAh/g. When the gram capacity of the multi-cation positive electrode material is too low, the high energy density of the battery cannot be realized; when the gram capacity is too high, the stability of the cathode material is lowered, resulting in an insufficient cycle life of the battery.
In some embodiments, in the multi-cation positive electrode material, the element of the L ion includes at least one of an alkali metal element, an alkaline earth metal element, a transition metal element, and other metal elements of the main group other than lithium element. Further, the alkali metal element includes at least one of Na, K, rb, cs; the alkaline earth metal element comprises at least one of Mg, ca and Sr; the transition metal element includes Y; and the main group other metal element includes Bi. In some embodiments, the L ions are different from other ions already present in the multi-cation positive electrode material, such as Co, ni, mn, and possibly M ions. In some embodiments, the elements of the L ion comprise at least two, optionally at least three, further optionally all four of Na, K, rb, cs. Optionally, the molar ratio of each of the at least two, three or four elements is greater than 0.5% based on the molar amount of Li ions. In some embodiments, the molar ratio of at least two of Na, K, rb, cs is greater than 0.005, e.g., from 0.01 to 0.25, based on the molar amount of Li ions. Specifically, the doping mole ratio of each element in the application can comprise the following technical scheme: na and K are not 0, or are both greater than 0.005; na and Rb are not 0 or are both greater than 0.005; na and Cs are not 0, or are both greater than 0.005; k and Rb are not 0 or are both greater than 0.005; k and Cs are not 0, or are both greater than 0.005; rb and Cs are not 0, or are both greater than 0.005; na, K and Rb are not 0 or are all more than 0.005; na, rb and Cs are not 0 or are all more than 0.005; na, K and Cs are not 0 or are all more than 0.005; K. rb and Cs are not 0, or are both greater than 0.005; na, K, rb and Cs are not 0 or are all greater than 0.005, all based on the molar amount of Li ions. The doping molar ratio of each element in Na, K, rb, cs may be the same, or may be different. For example, the polycationic positive electrode material of the present application may be Li0.96Na0.01K0.01Cs0.01Rb0.01Ni0.8Co0.1Mn0.1O2、Li0.94Na0.02K0.02Cs0.01Rb0.01Ni0.8Co0.1Mn0.1O2、Li0.96Na0.02K0.02Ni0.8Co0.1Mn0.1O2 or Li 0.97K0.01Cs0.01Rb0.01Ni0.8Co0.1Mn0.1O2. The values of the doping molar ratios of the respective elements Na, K, rb, cs can be achieved by adjusting the kinds and doping addition amounts of the respective elements, for example, by selecting specific doping elements and the relative molar amounts to be added respectively in the process of preparing the positive electrode material. The specific composition of the final positive electrode material may be determined by ICP or the like.
In some embodiments, in the multi-cation positive electrode material, a satisfies 0.5.ltoreq.a < 1; optionally, 0.8.ltoreq.a < 1.a represents the molar quantity proportion of lithium ions in the positive electrode material. Since a is less than 1, x is not 0, i.e., at least some of the lithium ions in the positive electrode material are replaced by at least one L ion, such as Na, K, rb, and Cs. In the alkali metal ion of the positive electrode material, the molar ratio of lithium ion is favorably adjusted to 50% or more, more favorably 80% or more. Too low a content of lithium ions, the lithium ion transport is hindered, resulting in a decrease in capacity and kinetics.
In some embodiments, in the multi-cation positive electrode material, 0.05.ltoreq.b.ltoreq.0.98, and 0.05.ltoreq.c.ltoreq.0.85. The values of b and c may be selected from a wide range depending on the desired materials, and are not particularly limited. Typically for high gram capacity cathode materials, the Ni content is relatively high, e.g. b may be above 0.5, above 0.6, even up to 0.98. The value of c may generally be from 0.05 to 0.3, alternatively from 0.1 to 0.2.
The M ion is a cation for partially substituting Ni, co and Mn, and includes at least one of Mg, zr, al, B, ta, mo, W, nb, sb, la. Alternatively, the M ion is selected from Mg, zr, al, B, ta, mo, W, nb, sb or La ions. The relative molar proportion of M ions may be from 0 to 20%, alternatively from 0 to 10%, based on the total molar amount of Ni, co and Mn. N ions are ions for doping a substitutional part of O ions, which include at least one of F, S and P; alternatively, it is selected from F, S or P. The doping amount of the N ion may be 0 to 20%, alternatively 0 to 5%, based on the molar amount of the O ion.
In some embodiments, the multi-cation positive electrode material may be prepared by the following method: firstly, preparing a conventional precursor by mixing compounds of lithium, cobalt, nickel and the like, then mixing, grinding and calcining the precursor and the compound of the doping element, and cooling to obtain the doped multi-cation positive electrode material. The compound may be a salt of each element, such as a carbonate salt. The charge of the compound containing each element may be determined according to the final composition of the desired positive electrode material, for example, by the molar ratio of each element in the final composition. The lithium salt is generally added in excess to compensate for losses during calcination.
A second aspect of the application provides a lithium ion battery comprising a positive electrode, wherein the positive electrode comprises a multi-cation positive electrode material according to the first aspect of the application. In general, the positive electrode material is coated on a positive electrode current collector to form a positive electrode active material layer. In the preparation of the positive electrode sheet, the positive electrode material, an adhesive, a conductive agent, etc. may be dispersed in an organic solvent such as N-methylpyrrolidone (NMP) to prepare a uniform slurry, coated on a positive electrode current collector, and then dried at a high temperature. The dried pole piece can be rolled and cut into a predetermined shape. The binder is not particularly limited, and may be exemplified by one or more of styrene-butadiene rubber (SBR), aqueous acrylic resin, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), ethylene-vinyl acetate copolymer (EVA), polyacrylic acid (PAA), carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA), and polyvinyl butyral (PVB). The kind of the conductive agent is not particularly limited either, and may be selected by those skilled in the art according to actual demands. As an example, the conductive agent for the positive electrode material may be selected from one or more of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers. In some embodiments, the slurry of the positive electrode sheet contains a positive electrode active material, a conductive agent, and a binder in a weight ratio of 70 to 90:5-15:5-15, optionally 75-85:8-12:8-12.
In some embodiments, the lithium ion battery comprises a negative electrode, and the negative electrode active material of the negative electrode comprises at least one of graphite, hard carbon, and soft carbon. However, the choice of the negative electrode material is not particularly limited, and a negative electrode material conventionally used for lithium ion batteries may be selected.
A third aspect of the application provides an electrical device comprising a lithium ion battery according to the second aspect of the application.
The composition and structure of the lithium ion battery will be described in detail.
The materials of the components of the lithium ion battery of the application can be selected within a wide range. In some embodiments, the battery is particularly a lithium ion secondary battery. Hereinafter, the battery cells of the lithium ion secondary battery will be described in detail.
In general, a lithium ion secondary battery includes a positive electrode tab, a negative electrode tab, a separator, and an electrolyte. During the charge and discharge of the battery, active ions are inserted and extracted back and forth between the positive electrode plate and the negative electrode plate. The diaphragm is arranged between the positive pole piece and the negative pole piece to play a role in isolation. The electrolyte plays a role in ion conduction between the positive electrode plate and the negative electrode plate.
[ Electrolyte ]
The electrolyte plays a role in ion conduction between the positive electrode plate and the negative electrode plate. The electrolyte includes an electrolyte salt and a solvent.
In the present application, the electrolyte salt may be a common electrolyte salt in a lithium ion secondary battery, such as a lithium salt, including the above-mentioned lithium salt as a high heat stability salt, a lithium salt as a low resistance additive, or a lithium salt that inhibits corrosion of aluminum foil. As an example, the electrolyte salt may be selected from one or more of lithium hexafluorophosphate (LiPF 6), lithium tetrafluoroborate (LiBF 4), lithium hexafluoroarsenate (LiAsF 6), lithium bis-fluorosulfonimide (LiFSI), lithium bis-trifluoromethanesulfonyl imide (LiTFSI), lithium trifluoromethanesulfonate (LiTFS), lithium difluorooxalato borate (lidadiob), lithium difluorophosphate (LiPO 2F2), lithium difluorodioxaoxalato phosphate (LiDFOP), lithium fluorosulfonate (LiSO 3 F), difluorooxalate (NDFOP), li 2F(SO2N)2SO2F、KFSI、CsFSI、Ba(FSI)2, and LiFSO 2NSO2CH2CH2CF3.
The kind of the solvent is not particularly limited and may be selected according to actual demands. In some embodiments, the solvent is a non-aqueous solvent. Alternatively, the solvent may comprise one or more of a chain carbonate, a cyclic carbonate, a carboxylic acid ester. In some embodiments, the solvent may be selected from one or more of Ethylene Carbonate (EC), propylene Carbonate (PC), ethylmethyl carbonate (EMC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), butylene Carbonate (BC), fluoroethylene carbonate (FEC), methyl Formate (MF), methyl Acetate (MA), ethyl Acetate (EA), propyl Acetate (PA), methyl Propionate (MP), ethyl Propionate (EP), propyl Propionate (PP), methyl Butyrate (MB), ethyl Butyrate (EB), 1, 4-butyrolactone (GBL), tetrahydrofuran, sulfolane (SF), dimethylsulfone (MSM), methylsulfone (EMS), and diethylsulfone (ESE).
In some embodiments, other additives may also be optionally included in the electrolyte. For example, the additives may include negative electrode film-forming additives, or may include positive electrode film-forming additives, or may include additives that improve certain properties of the battery, such as additives that improve the overcharge properties of the battery, additives that improve the high temperature properties of the battery, additives that improve the low temperature properties of the battery, and the like. As an example, the additive is selected from at least one of a cyclic carbonate compound containing an unsaturated bond, a halogen-substituted cyclic carbonate compound, a sulfate compound, a sulfite compound, a sultone compound, a disulfonic acid compound, a nitrile compound, an aromatic compound, an isocyanate compound, a phosphazene compound, a cyclic anhydride compound, a phosphite compound, a phosphate compound, a borate compound, and a carboxylate compound.
[ Positive electrode sheet ]
The positive electrode sheet comprises a positive electrode current collector and a positive electrode active material layer arranged on at least one surface of the positive electrode current collector, wherein the positive electrode active material layer comprises a positive electrode active material and a conductive agent.
As an example, the positive electrode current collector has two surfaces opposing in its own thickness direction, and the positive electrode active material layer is provided on either one or both of the two surfaces opposing the positive electrode current collector.
In the lithium ion secondary battery of the application, the positive electrode current collector can adopt a metal foil or a composite current collector. For example, as the metal foil, aluminum foil may be used. The composite current collector may include a polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base layer. The composite current collector may be formed by forming a metal material (e.g., aluminum alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a polymer material substrate (e.g., a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
The positive electrode active material layer disposed on the surface of the positive electrode current collector includes a positive electrode active material. The positive electrode active material used in the present application may have any conventional positive electrode active material used in secondary batteries. In some embodiments, the positive electrode active material may include one or more selected from lithium transition metal oxides, olivine structured lithium-containing phosphates, and their respective modified compounds. Examples of the lithium transition metal oxide may include, but are not limited to, one or more of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt aluminum oxide, and modified compounds thereof. Examples of olivine structured lithium-containing phosphates may include, but are not limited to, one or more of lithium iron phosphate, lithium iron phosphate-carbon composites, lithium manganese phosphate-carbon composites, lithium manganese phosphate-iron, lithium manganese phosphate-carbon composites, and modified compounds thereof. These materials are commercially available. The surface of the positive electrode active material may be coated with carbon. The positive electrode active material may be doped to obtain a doped positive electrode active material. The doping element may include at least one selected from Na, K, rb, and Cs, but is not limited thereto.
The positive electrode active material layer optionally includes a conductive agent. However, the kind of the conductive agent is not particularly limited, and one skilled in the art may select according to actual needs. As an example, the conductive agent for the positive electrode material may be selected from one or more of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
The positive electrode active material layer further includes an aqueous binder. The aqueous binder may be selected from one or more of soluble polysaccharides and derivatives thereof, and water-soluble or water-dispersible polymers. As examples, the aqueous binder may be methylcellulose and salts thereof, xanthan gum and salts thereof, chitosan and salts thereof, alginic acid and salts thereof; polyethyleneimine and salts thereof, polyacrylamide, acrylic acid copolymer and derivatives thereof.
The positive electrode sheet may be prepared according to methods known in the art. As an example, the carbon-coated positive electrode active material, the conductive agent, and the aqueous binder may be dispersed in a solvent (e.g., water) to form a uniform positive electrode slurry; and (3) coating the positive electrode slurry on a positive electrode current collector, and obtaining a positive electrode plate after the procedures of drying, cold pressing and the like.
[ Negative electrode sheet ]
The negative electrode tab includes a negative electrode current collector and a negative electrode material layer disposed on at least one surface of the negative electrode current collector, the negative electrode material layer including a negative electrode active material.
As an example, the anode current collector has two surfaces opposing in its own thickness direction, and the anode material layer is provided on either one or both of the two surfaces opposing the anode current collector.
In the lithium ion secondary battery of the application, the negative electrode current collector can adopt a metal foil or a composite current collector. For example, as the metal foil, copper foil may be used. The composite current collector may include a polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base material. The composite current collector may be formed by forming a metal material (e.g., copper alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a polymer material substrate (e.g., a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In the lithium ion secondary battery of the present application, the negative electrode material layer generally contains a negative electrode active material, and optionally a binder, an optional conductive agent, and other optional auxiliary agents, and is generally formed by coating and drying a negative electrode slurry. The negative electrode slurry coating is generally formed by dispersing a negative electrode active material, an optional conductive agent, a binder, and the like in a solvent and stirring uniformly. The solvent may be N-methylpyrrolidone (NMP) or deionized water.
The specific kind of the negative electrode active material is not limited, and an active material known in the art to be capable of being used for a negative electrode of a lithium ion secondary battery may be used, and those skilled in the art may select according to actual demands. As an example, the negative electrode active material may be selected from one or more of graphite, soft carbon, hard carbon, mesophase carbon microspheres, carbon fibers, carbon nanotubes, elemental silicon, silicon oxygen compounds, silicon carbon composites, lithium titanate.
As an example, the conductive agent may be selected from one or more of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
As an example, the binder may be selected from one or more of Styrene Butadiene Rubber (SBR), polyacrylic acid (PAA), sodium Polyacrylate (PAAs), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium Alginate (SA), polymethacrylic acid (PMAA), and carboxymethyl chitosan (CMCS).
Other optional adjuvants are, for example, thickeners such as sodium carboxymethylcellulose (CMC-Na), etc.
[ Diaphragm ]
A lithium ion secondary battery using the electrolyte includes a separator. The diaphragm is arranged between the positive pole piece and the negative pole piece to play a role in isolation. The separator of the present application is as described above; however, the lithium ion battery of the present application may further comprise a conventional separator. The kind of the conventional separator is not particularly limited, and any known porous structure separator having good chemical stability and mechanical stability may be selected. In some embodiments, the material of the conventional separator may be selected from more than one of glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride. The separator may be a single-layer film or a multilayer composite film, and is not particularly limited. When the separator is a multilayer composite film, the materials of the respective layers may be the same or different, and are not particularly limited.
In some embodiments, the positive electrode tab, the negative electrode tab, and the separator may be manufactured into an electrode assembly through a winding process or a lamination process.
In some embodiments, the secondary battery may include an outer package. The outer package may be used to encapsulate the electrode assembly and electrolyte described above.
In some embodiments, the outer package of the secondary battery may be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, or the like. The exterior package of the secondary battery may also be a pouch, such as a pouch-type pouch. The material of the flexible bag may be plastic, and examples of the plastic include polypropylene (PP), polybutylene terephthalate (PBT), and polybutylene succinate (PBS).
The shape of the secondary battery is not particularly limited in the present application, and may be cylindrical, square, or any other shape. For example, fig. 1 is a lithium ion secondary battery 5 of a square structure as an example.
In some embodiments, referring to fig. 2, the outer package may include a housing 51 and a cover 53. The housing 51 may include a bottom plate and a side plate connected to the bottom plate, where the bottom plate and the side plate enclose a receiving chamber. The housing 51 has an opening communicating with the accommodation chamber, and the cover plate 53 can be provided to cover the opening to close the accommodation chamber. The positive electrode sheet, the negative electrode sheet, and the separator may be formed into the electrode assembly 52 through a winding process or a lamination process. The electrode assembly 52 is enclosed in the accommodating chamber. The electrolyte is impregnated in the electrode assembly 52. The number of electrode assemblies 52 included in the lithium ion secondary battery 5 may be one or more, and those skilled in the art may select according to specific practical requirements.
In some embodiments, the lithium ion secondary batteries may be assembled into a battery module 4, and the number of lithium ion secondary batteries contained in the battery module 4 may be one or more, and the specific number may be selected by one skilled in the art according to the application and capacity of the battery module 4. In the battery module 4, a plurality of lithium ion secondary batteries 5 may be arranged in order along the longitudinal direction of the battery module. Of course, the arrangement may be performed in any other way. The plurality of lithium ion secondary batteries 5 may be further fixed by fasteners. Alternatively, the battery module 4 may further include a case having an accommodating space in which the plurality of lithium ion secondary batteries 5 are accommodated.
In some embodiments, the lithium ion secondary batteries 5 or the battery modules 4 may be assembled into the battery pack 1, and the number of the lithium ion secondary batteries 5 or the battery modules 4 included in the battery pack 1 may be selected by one skilled in the art according to the application and the capacity of the battery pack 1.
The lithium ion secondary battery of the present application may include a battery cell form, a battery module form, or a battery pack form. In some embodiments, the battery cells may be assembled into a battery module. In some embodiments, the above-described battery cells may be assembled into a battery pack. In some embodiments, the battery module may be assembled into a battery pack.
Fig. 3 and 4 are battery packs 1 as an example. Referring to fig. 3 and 4, a battery case and a plurality of battery cells disposed in the battery case may be included in the battery pack 1. The battery box comprises an upper box body 2 and a lower box body 3, wherein the upper box body 2 can be covered on the lower box body 3, and a closed space for accommodating the battery monomers is formed.
In addition, the application also provides a device which comprises the battery pack provided by the application. The battery pack may be used as a power source for the device and may also be used as an energy storage unit for the device. The device may be, but is not limited to, a mobile device (e.g., a cell phone, a notebook computer, etc.), an electric vehicle (e.g., a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, an electric bicycle, an electric scooter, an electric golf cart, an electric truck, etc.), an electric train, a watercraft, a satellite, an energy storage system, etc. As the device, a battery pack may be selected according to its use requirement.
Fig. 5 is an apparatus as one example. The device is a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle or the like. In order to meet the high power and high energy density requirements of the device for lithium ion secondary batteries, a battery pack or a battery module may be employed.
Examples
Hereinafter, embodiments of the present application are described. The following examples are illustrative only and are not to be construed as limiting the application. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. Unless otherwise indicated, all experimental steps were carried out at normal pressure.
Example 1
Preparation of doped high-nickel positive electrode material Li 0.96Na0.01K0.01Cs0.01Rb0.01Ni0.8Co0.1Mn0.1O2
Firstly, nickel acetate, cobalt acetate and manganese acetate are added into deionized water according to stoichiometric ratio, and are stirred uniformly. The sodium carbonate solution is rapidly poured into the transition metal salt solution, the reaction is continued for 9 hours, and then the mixture is kept stand and aged for 4 hours, so as to enable primary particles to grow. Washing with deionized water for 3 times, drying in a blast drier, vacuum drying at 100deg.C for 12h, and collecting dried solid as precursor.
Mixing the precursor with lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate and cesium carbonate according to a molar ratio of 1: uniformly mixing at a ratio of 1.05:0.01:0.01:0.01:0.01, and grinding. The excess lithium carbonate is to compensate for the loss of lithium during high temperature calcination. And transferring the fully ground solid powder to a crucible, and placing the crucible in a muffle furnace with programmed temperature for calcination. The calcination procedure is as follows: pre-calcining for 5h from room temperature to 500 ℃, and calcining for 12h at 800 ℃ with the temperature rising rate of 3 ℃ min -1. The resulting material was collected after subsequent cooling to room temperature.
[ Preparation of Positive electrode sheet ]
Mixing the positive electrode material prepared in the above way with polyvinylidene fluoride (PVDF) and a conductive agent (carbon black Super P) according to a mass ratio of 90:5:5, taking N methyl-pyrrolidone (NMP) as a solvent, and adjusting the addition amount of the solvent to control the viscosity of the slurry to be 100-20000 Pa.s. The slurry was coated on the surface of an aluminum foil using a coater, and then transferred to a vacuum drying oven to be completely dried. And (3) drying at 85 ℃, cold pressing, trimming, cutting pieces, splitting, drying at 85 ℃ under vacuum for 4 hours, and welding the tab to prepare the positive electrode plate. The total coating amount of the positive electrode active material on the obtained electrode sheet was 0.3g/1540.25mm 2.
[ Preparation of negative electrode sheet ]
Adding active substance graphite, conductive agent Super-P, thickener CMC and binder SBR into solvent deionized water according to the mass ratio of 96.5:1.0:1.0:1.5, and uniformly mixing to prepare anode slurry; coating anode slurry on a current collector copper foil, drying at 85 ℃, trimming, cutting pieces, splitting, drying at 110 ℃ under vacuum for 4 hours, and welding tabs to prepare a negative electrode plate.
[ Preparation of electrolyte ]
The method comprises the steps of taking a mixture of Ethylene Carbonate (EC), propylene Carbonate (PC) and diethyl carbonate (DEC) as a nonaqueous organic solvent, wherein the mass ratio of the components is EC to PC to DEC=30 to 30 to 40, and lithium hexafluorophosphate (LiPF 6) is taken as lithium salt, so that an electrolyte with the concentration of 1M is prepared.
[ Isolation Membrane ]
A12 μm polypropylene film was used as a separator.
[ Preparation of lithium ion Battery ]
The positive electrode plate, the isolating film and the negative electrode plate are sequentially stacked, so that the isolating film is positioned between the positive electrode plate and the negative electrode plate to play a role of isolation, and the electrolyte is added to assemble the laminated battery, namely the lithium ion secondary battery in the embodiment 1.
Example 2
Preparation of doped high-nickel positive electrode material Li 0.96Na0.04Ni0.8Co0.1Mn0.1O2
Firstly, nickel acetate, cobalt acetate and manganese acetate are added into deionized water according to stoichiometric ratio, and are stirred uniformly. The sodium carbonate solution is rapidly poured into the transition metal salt solution, the reaction is continued for 9 hours, and then the mixture is kept stand and aged for 4 hours, so as to enable primary particles to grow. Washing with deionized water for 3 times, drying in a blast drier, vacuum drying at 100deg.C for 12h, and collecting dried solid as precursor.
The precursor, lithium carbonate and sodium carbonate are uniformly mixed according to the mol ratio of 1:1.05:0.04, and then ground. The excess lithium carbonate is to compensate for the loss of lithium during high temperature calcination. And transferring the fully ground solid powder to a crucible, and placing the crucible in a muffle furnace with programmed temperature for calcination. The calcination procedure is as follows: pre-calcining for 5h from room temperature to 500 ℃, and calcining for 12h at 800 ℃ with the temperature rising rate of 3 ℃ min -1. The resulting material was collected after subsequent cooling to room temperature.
The lithium ion battery of example 2 was prepared in the same manner as described in example 1, except that the positive electrode material used was the positive electrode material prepared according to the description of example 2.
Comparative example 1
Preparation of undoped cathode material LiNi0 .8Co0.1Mn0.1O2
Firstly, nickel acetate, cobalt acetate and manganese acetate are added into deionized water according to stoichiometric ratio, and are stirred uniformly. The sodium carbonate solution is rapidly poured into the transition metal salt solution, the reaction is continued for 9 hours, and then the mixture is kept stand and aged for 4 hours, so as to enable primary particles to grow. Washing with deionized water for 3 times, drying by a blast drier, vacuum drying at 100 ℃ for 12 hours, and collecting dried solid to obtain a precursor.
The precursor and lithium carbonate are uniformly mixed according to the mol ratio of 1:1.07, and then ground. The excess lithium carbonate is to compensate for the loss of lithium during high temperature calcination. And transferring the fully ground solid powder to a crucible, and placing the crucible in a muffle furnace with programmed temperature for calcination. The calcination procedure is as follows: pre-calcining for 5h from room temperature to 500 ℃, and calcining for 12h at 800 ℃ with the temperature rising rate of 3 ℃ min -1. The resulting material was collected after subsequent cooling to room temperature.
The lithium ion battery of comparative example 1 was prepared in the same manner as described in example 1, except that the positive electrode material used was the positive electrode material prepared according to comparative example 1.
Comparative example 2
Preparation of cathode material Li 0.4Na0.6Ni0.8Co0.1Mn0.1O2
Firstly, nickel acetate, cobalt acetate and manganese acetate are added into deionized water according to stoichiometric ratio, and are stirred uniformly. The sodium carbonate solution is rapidly poured into the transition metal salt solution, the reaction is continued for 9 hours, and then the mixture is kept stand and aged for 4 hours, so as to enable primary particles to grow. Washing with deionized water for 3 times, drying by a blast drier, vacuum drying at 100 ℃ for 12 hours, and collecting dried solid to obtain a precursor.
The precursor, lithium carbonate and sodium carbonate are uniformly mixed according to the mol ratio of 1:0.43:0.6, and then ground. The excess lithium carbonate is to compensate for the loss of lithium during high temperature calcination. And transferring the fully ground solid powder to a crucible, and placing the crucible in a muffle furnace with programmed temperature for calcination. The calcination procedure is as follows: pre-calcining for 5h from room temperature to 500 ℃, and calcining for 12h at 800 ℃ with the temperature rising rate of 3 ℃ min -1. The resulting material was collected after subsequent cooling to room temperature.
The lithium ion battery of comparative example 2 was prepared in the same manner as described in example 1, except that the positive electrode material used was the positive electrode material prepared according to comparative example 2.
Comparative example 3
Preparation of cathode material Li 0.9996Na0.0004Ni0.8Co0.1Mn0.1O2
Firstly, nickel acetate, cobalt acetate and manganese acetate are added into deionized water according to stoichiometric ratio, and are stirred uniformly. The sodium carbonate solution is rapidly poured into the transition metal salt solution, the reaction is continued for 9 hours, and then the mixture is kept stand and aged for 4 hours, so as to enable primary particles to grow. Washing with deionized water for 3 times, drying by a blast drier, vacuum drying at 100 ℃ for 12 hours, and collecting dried solid to obtain a precursor.
The precursor, lithium carbonate and sodium carbonate are mixed uniformly according to the mol ratio of 1:1.07:0.0004, and then ground. The excess lithium carbonate is to compensate for the loss of lithium during high temperature calcination. And transferring the fully ground solid powder to a crucible, and placing the crucible in a muffle furnace with programmed temperature for calcination. The calcination procedure is as follows: pre-calcining for 5h from room temperature to 500 ℃, and calcining for 12h at 800 ℃ with the temperature rising rate of 3 ℃ min -1. The resulting material was collected after subsequent cooling to room temperature.
The lithium ion battery of comparative example 3 was prepared in the same manner as described in example 1, except that the positive electrode material used was the positive electrode material prepared according to comparative example 3.
[ Battery Performance test ]
1. Gram capacity of positive electrode material
The button cell was fabricated, charged at constant voltage after constant current at 0.1C, discharged at 0.1C, and the capacity was measured, divided by the mass of active material to obtain gram capacity.
2. And (3) testing the cycle performance:
the cycle number test conditions were: the secondary battery was subjected to 1C/1C cycle test at 25℃and 45℃with a charge-discharge voltage ranging from 2.8 to 4.35V, and the test was stopped when the capacity was decayed to 80% of the first discharge specific capacity.
The lithium ion batteries prepared in examples 1-2 and comparative examples 1-3 were subjected to the performance test as described above, and the test results are summarized in table 1 below.
TABLE 1
From the results shown in table 1, it can be seen that the structural stability of the positive electrode material can be effectively improved and the cycle life of the lithium ion battery can be improved by doping and substituting the Li ions in the positive electrode material to a certain extent by using the cations L with larger ionic radius. In addition, the ratio of the molar amount of the doping element to the gram-volume is controlled within a certain range. An overdose (comparative example 2) and an underdose (comparative example 3) may result in an insufficient improvement effect on the cycle life of the lithium ion battery.
While the application has been described with reference to an exemplary embodiment, various modifications may be made and equivalents may be substituted for elements thereof without departing from the scope of the application. In particular, the technical features mentioned in the respective embodiments may be combined in any manner as long as there is no structural conflict. The present application is not limited to the specific embodiments disclosed herein, but encompasses all technical solutions falling within the scope of the claims.
Claims (12)
1. A multi-cation positive electrode material is provided, which has a general formula of Li aLxNibCocMndM(1-b-c-d)OeNf or mLi2MnO3·(1-m)LiaLxNibCocMndM(1-b-c-d)OeNf,, wherein L ions are cations with a radius larger than that of Li ions, M comprises at least one of Mg, zr, al, B, ta, mo, W, nb, sb, la, N comprises at least one of F, S and P, 0 < a < 1,0 < b < 1,0 < c < 1,0 < d < 1,0 < b+c+d < 1,0 < e < 2,0 < f < 2,0 < M < 1,0 < x < 0.8, a+x=1, e+f=2,
And satisfies the following relationship:
2.5 x 10 -6≤x/v≤2.5×10-3, wherein v is the gram capacity of the polycationic positive electrode material.
2. The positive electrode material according to claim 1, wherein 0.001 < x.ltoreq.0.5; optionally 0.003 < x.ltoreq.0.05.
3. The positive electrode material according to claim 1 or 2, wherein x and v satisfy the following formula:
2.5×10-5≤x/v≤2.5×10-4。
4. The positive electrode material according to any one of claims 1 to 3, wherein a gram capacity v of the positive electrode material satisfies 120 mAh/g+.v+.300 mAh/g.
5. The positive electrode material according to any one of claims 1 to 4, wherein an element of the L ion includes at least one of an alkali metal element, an alkaline earth metal element, a transition metal element, and other metal elements of main group other than a lithium element.
6. The positive electrode material according to claim 5, wherein the alkali metal element comprises at least one of Na, K, rb, cs; the alkaline earth metal element comprises at least one of Mg, ca and Sr; the transition metal element includes Y; and the main group other metal element includes Bi.
7. The positive electrode material according to claim 5 or 6, wherein the element of L ion includes at least two of Na, K, rb, cs; preferably, the molar ratio of each of the at least two elements is greater than 0.5% based on the molar amount of Li ions.
8. The positive electrode material according to any one of claims 1 to 7, wherein a satisfies 0.5.ltoreq.a < 1; optionally, 0.8.ltoreq.a < 1.
9. The positive electrode material according to any one of claims 1 to 8, wherein 0.05+.b+.0.98, and 0.05+.c+.0.85.
10. A lithium ion battery comprising a positive electrode comprising the multi-cation positive electrode material according to any one of claims 1 to 9.
11. The lithium ion battery of claim 10, comprising a negative electrode, a negative electrode active material of the negative electrode comprising at least one of graphite, hard carbon, and soft carbon.
12. An electrical device comprising the lithium ion battery of claim 10 or 11.
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| CN202310366399.4A CN118825256A (en) | 2023-04-07 | 2023-04-07 | Positive electrode material, battery comprising same and power utilization device |
| PCT/CN2024/086364 WO2024208355A1 (en) | 2023-04-07 | 2024-04-07 | Positive electrode material and battery comprising same, and electric device |
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| JPH0714579A (en) * | 1993-06-25 | 1995-01-17 | Fuji Photo Film Co Ltd | Nonaqueous electrolyte secondary battery |
| JP3230893B2 (en) * | 1993-04-28 | 2001-11-19 | 富士写真フイルム株式会社 | Non-aqueous electrolyte secondary battery |
| JP5904371B2 (en) * | 2010-09-22 | 2016-04-13 | 株式会社Ｇｓユアサ | Active material for lithium secondary battery, electrode for lithium secondary battery, and lithium secondary battery |
| CN104882592B (en) * | 2014-02-27 | 2019-08-30 | 松下知识产权经营株式会社 | Positive electrode active material for nonaqueous electrolyte secondary battery and its manufacturing method and non-aqueous electrolyte secondary battery |
| CN103915617A (en) * | 2014-04-18 | 2014-07-09 | 东莞市迈科科技有限公司 | Lithium-rich positive material and preparation method thereof |
| CN111463428A (en) * | 2020-04-15 | 2020-07-28 | 江南大学 | Sodium ion doped ternary cathode material and preparation method thereof |
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