CN116435477A - Positive electrode material, positive electrode sheet and battery - Google Patents
Positive electrode material, positive electrode sheet and battery Download PDFInfo
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- CN116435477A CN116435477A CN202310319966.0A CN202310319966A CN116435477A CN 116435477 A CN116435477 A CN 116435477A CN 202310319966 A CN202310319966 A CN 202310319966A CN 116435477 A CN116435477 A CN 116435477A
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- positive electrode
- electrode material
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Images
Classifications
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/362—Composites
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H—ELECTRICITY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The application relates to the technical field of batteries, in particular to a positive electrode material, a positive electrode plate and a battery. The positive electrode material comprises a matrix and a coating layer; the coating layer includes a compound containing Li, nb, and W elements. The compound containing Li, nb and W elements is arranged on the surface of the matrix, so that the surface of the positive electrode material can be optimized, the impedance is reduced, and the cycle stability and the thermal stability of the lithium ion battery are improved.
Description
Technical Field
The application relates to the technical field of batteries, in particular to a positive electrode material, a positive electrode plate and a battery.
Background
In lithium ion batteries, as the energy density requirements increase and the operating voltage requirements increase over the last two decades, there is a continuing need to address the problems and challenges that follow.
Under high voltage, a great deal of lithium extraction can lead to the gradual unbalance of charge balance inside the material, various phase changes occur after the lithium extraction, and lithium atoms are extracted from the surface, so that the quantity of lithium in the surface structure is smaller than that of the bulk phase structure during long-time charging, and obviously, the requirement of the surface structure on the structural stability is far higher than that of the bulk phase structure, namely, a phase change inhibition strategy special for the surface layer lithium-containing positive electrode material is needed. The common strategy is to coat the surface of the positive electrode material, and a plurality of coating materials exist at present, but the affinity with the positive electrode material is limited, and the positive electrode material is easy to fall off under long circulation, so that random failure is caused.
Disclosure of Invention
In view of this, the present invention provides a positive electrode material, a positive electrode sheet, and a battery. The positive electrode material has good bulk phase and surface structure stability under high voltage, so that the cycle stability and the thermal stability of the lithium ion battery under high voltage are improved.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a positive electrode material, which comprises a matrix and a coating layer;
the coating layer includes a compound containing Li (lithium), nb (niobium), and W (tungsten).
Preferably, the compound containing Li, nb and W elements includes Li d Nb e W f O 6 ，
Wherein d is more than 0.95 and less than 1.05,0.95, e is more than 1.05,0.95 and f is more than 1.05;
preferably, the Li, nb and W element-containing compound is lithium niobium tungsten oxide LiNbWO 6 。
More preferably, the Li, nb and W element-containing compound is a lithium niobium tungsten oxide compound LiNbWO having a structure of P-421m 6 。
Preferably, the mass content of the compound containing Li, nb, and W elements in the positive electrode material is 0.02% to 1%. For example, the value may be any one of 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1% or a range between any two of the values. The positive electrode material in the content range has higher discharge gram capacity and better multiplying power performance, and is beneficial to improving the cycle stability and the thermal stability of the material. When the content of the compound containing Li, nb and W is too large, the discharge gram capacity is reduced, and the rate performance is deteriorated; when the content of the compound containing Li, nb, W is too small, the effect of improving the surface of the base material and the interface stability with the electrolyte at high voltage is not remarkable, and the improvement of the cycle stability and the thermal stability of the material is not facilitated.
Preferably, the thickness of the coating layer is 10-50 nm.
Preferably, the coating layer further comprises a spinel structure compound.
Preferably, the spinel structure compound has the chemical formula AB 2-m C m O 4 ，
Wherein m is more than or equal to 0 and less than 0.01, A and B are respectively and independently selected from one of Al, mg, ti, co, ni, A and B are different, and C is selected from at least one of Al, mg, ti, W, nb, mo, te, ce.
Preferably, the mass content of the spinel structure compound in the positive electrode material is 0.02% -1%; for example, the value may be any one of 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1% or a range between any two of the values. The positive electrode material within the content range of the spinel-structured compound has higher discharge gram capacity and better multiplying power performance, and is beneficial to improving the cycle stability and the thermal stability of the material. When the spinel-structured compound content is too large, the discharge gram capacity is lowered, deteriorating the rate performance; when the content of the spinel-structured compound is too small, the effect of improving the surface of the base material and the interface stability with the electrolyte is not obvious at high voltage, which is unfavorable for improving the cycle stability and the thermal stability of the material.
In a particular embodiment provided by the present invention, the spinel structure compound is NiCo 1.995 W 0.005 O 4 Or NiCo 1.995 Ti 0.005 O 4 。
In an embodiment of the present invention, the coating layer is one coating layer or two coating layers.
Preferably, the coating layer is two layers of coating layers, the coating layer comprising spinel structure compound is a first coating layer, and the first coating layer is arranged on the surface of the substrate; the coating layer including a compound containing Li, nb, and W elements is a second coating layer provided on the surface of the substrate coated with the first coating layer.
The spinel structure compound is coated on the surface of the matrix material, and the coating is completely coating or partially coating. After the spinel structure compound is coated on the surface of the positive electrode material, the stability of the surface interface structure of the positive electrode material in the circulation process under high voltage can be relieved, the formation of microcracks is reduced, and the circulation performance and the safety performance of the positive electrode material are improved.
The compound containing Li, nb and W is coated on the surface of the spinel structure compound, and the coating is completely or partially coated. By adopting the surface-coated lithium-niobium-tungsten-oxygen fast ion conductor compound, the high valence ion radius W in the fast ion conductor compound 6+ And Nb (Nb) 5+ Can permeate into the surface layer of the positive electrode material, increases the interlayer spacing, and is favorable for improving the lithium ion diffusion performance of the surface of the positive electrode material, thereby improving the dynamic performance. In addition, the lithium niobium tungsten oxygen fast ion conductor compound can provide an additional lithium source and has a certain lithium supplementing effect, so that the gram capacity of the positive electrode material is improved.
The spinel structure compound is arranged on the surface of the matrix, so that the structure of the positive electrode material under high voltage can be stabilized, and a gradient doping structure from the surface to the bulk phase can be formed on the surface of the matrix in the synthesis process, thereby improving the bulk phase structure stability of the positive electrode material; the compound containing Li, nb and W elements is arranged on the surface of the spinel structure compound, so that the surface of the positive electrode material can be further optimized, the impedance is reduced, and the cycle stability and the thermal stability of the lithium ion battery are improved.
Preferably, the thickness of the first coating layer is 5 to 30nm; for example, the value is any one of 5nm, 6nm, 8nm, 10nm, 12nm, 14nm, 16nm, 18nm, 20nm, 22nm, 24nm, 26nm, 28nm, 30nm or a range between any two of the values. The positive electrode material within the thickness range has higher discharge gram capacity and better multiplying power performance, and is beneficial to improving the cycle stability and the thermal stability of the material. When the thickness is too large, the discharge gram capacity is reduced, and the rate performance is deteriorated; when the thickness is too small, the effect of improving the surface of the base material and the stability of the interface with the electrolyte is not obvious at high voltage, which is unfavorable for improving the cycle stability and the thermal stability of the material.
Preferably, the thickness of the second coating layer is 5-30 nm; for example, the value is any one of 5nm, 6nm, 8nm, 10nm, 12nm, 14nm, 16nm, 18nm, 20nm, 22nm, 24nm, 26nm, 28nm, 30nm or a range between any two of the values. The positive electrode material within the thickness range has higher discharge gram capacity and better multiplying power performance, and is beneficial to improving the cycle stability and the thermal stability of the material. When the thickness is too large, the discharge gram capacity is reduced, and the rate performance is deteriorated; when the thickness is too small, the effect of improving the surface of the base material and the stability of the interface with the electrolyte is not obvious at high voltage, which is unfavorable for improving the cycle stability and the thermal stability of the material.
Preferably, the sum of the thicknesses of the first coating layer and the second coating layer is 10 to 50nm. For example, the value may be any one of 10nm, 12nm, 14nm, 16nm, 18nm, 20nm, 22nm, 24nm, 26nm, 28nm, 30nm, 32nm, 34nm, 36nm, 38nm, 40nm, 42nm, 44nm, 46nm, 48nm, or 50nm or a range between any two of the values. The positive electrode material within the thickness range has higher discharge gram capacity and better multiplying power performance, and is beneficial to improving the cycle stability and the thermal stability of the material. When the thickness is too large, the discharge gram capacity is reduced, and the rate performance is deteriorated; when the thickness is too small, the effect of improving the surface of the base material and the stability of the interface with the electrolyte is not obvious at high voltage, which is unfavorable for improving the cycle stability and the thermal stability of the material.
In the embodiment of the invention, the matrix is doped with an element A and an element B, wherein A and B are respectively and independently selected from one of Al, mg, ti, co, ni, and A and B are different; the A element and the B element are in a gradient doping state in the matrix, and the gradient doping is gradually decreased from the surface to the bulk phase.
According to an embodiment of the invention, AB 2-m C m O 4 And Li (lithium) d Nb e W f O 6 Introduced during the second sintering or the third sintering, during the sintering, AB 2-m C m O 4 The element A and the element B in the material can be uniformly diffused to the surface layer of the matrix material, and the gradient doping characteristic is presented, and the diffusion of the element A can well inhibit the H1-3 phase change under high voltage (namely the high delithiation state of the material), and the element AB 2-m C m O 4 Not only can the stability of the surface structure be improved, but also the oxidative decomposition of the electrolyte and the accumulation of surface byproducts caused by the strong oxidizing property of the matrix material in the high Li removal state under high voltage can be relieved, the dissolution of transition metal elements on the surface of the matrix material and the surface structure damage are inhibited, and the interface stability of the electrolyte and the matrix material under high voltage can be further improved; meanwhile, the fast ion conductor coating layer is favorable for the diffusion of lithium ions, so that the dynamic performance is improved, and the lithium niobium tungsten oxide compound Li d Nb e W f O 6 Additional lithium sources can be provided in the charge and discharge process, so that the capacity in the charge and discharge process is ensured. Thus AB 2-m C m O 4 And Li (lithium) d Nb e W f O 6 The coating of the matrix material improves the structural stability and thermal stability of the matrix material, thereby improving the electrochemical performance at high voltages.
In an embodiment of the present invention, the matrix comprises one or more of transition metal lithium oxide, lithium iron phosphate, lithium iron manganese phosphate, and lithium-rich manganese-based materials.
Preferably, the matrix has the chemical formula Li x1 Co 1-x-y Al x M y O 2 And/or Li x2 Ni 1-a-b-z Co a R b N z O 2 ，
Wherein x is more than 0.95 and less than or equal to 1 and less than or equal to 1.05,0.03 and less than or equal to 0.05 or x= 0,0.0005 and less than or equal to y and less than or equal to 0.01, and M comprises at least one of Mg, mn, ni, ti, la, Y, zr, W, nb, te, ce; r comprises Mn and/or Al;
x2 is more than 0.95 and less than 1.05,0, a is more than or equal to 1/3, b is more than or equal to 0 and less than or equal to 1/3, z is more than or equal to 0 and less than or equal to 0.01, and N is at least one of Mn, al, mg, ti, zr, W, nb, B, la, Y, mo, si;
preferably, 0.ltoreq.a+b.ltoreq.0.5.
Preferably, the particle diameter D50 of the positive electrode material is 3-20 μm; for example, the value may be any one of 3 μm, 4 μm, 6 μm, 8 μm, 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, or 20 μm or a range between any two of the values. Within this range, the positive electrode material D50 can be compacted and the rate performance can be considered.
In one embodiment of the invention, the matrix has the chemical formula Li x1 Co 1-x-y Al x M y O 2 When the particle diameter D50 of the positive electrode material is 10-20 mu m; for example, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm,
Any one value or any range between two values of 20 μm. The positive electrode material D50 is within this range, and the positive electrode material can be compacted and the rate performance can be considered.
In another embodiment of the present invention, the matrix has the chemical formula Li x2 Ni 1-a-b-z Co a Mn b N z O 2 When the particle diameter D50 of the positive electrode material is 3-15 mu m. For example, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm,
Any one value or range of values between any two values of 13 μm, 14 μm and 15 μm. The positive electrode material D50 is within this range, and the positive electrode material can be compacted and the rate performance can be considered.
Preferably, the positive electrode material has a compacted density of 3.5 to 5g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the For example 3.5g/cm 3 、3.6g/cm 3 、3.8g/cm 3 、4g/cm 3 、4.2g/cm 3 、4.4g/cm 3 、
4.6g/cm 3 、4.8g/cm 3 、5g/cm 3 Any one of the values or a range between any two of the values. In this compacted density range, the positive electrode material has a higher compacted density, so that the battery has a higher battery capacity and better cycle performance. Too high a compaction density will result in too tight contact between the particles of material and enhanced electron conductivity, but reduced ion transport channels, increased polarization during discharge and reduced voltageFast, capacity reduction; the compaction density is too small, the distance between particles is large, the electrolyte is absorbed more, the movement of ions is facilitated, the contact area between particles is small, the electron conduction capacity is reduced, and the discharge electrode is increased.
In one embodiment of the invention, the matrix has the chemical formula Li x1 Co 1-x-y Al x M y O 2 When the positive electrode material is compacted, the density is 3.5-4.5 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the For example 3.5g/cm 3 、3.6g/cm 3 、3.8g/cm 3 、4g/cm 3 、4.2g/cm 3 、4.4g/cm 3 、4.5g/cm 3 Any one of the values or a range between any two of the values. In this compacted density range, the positive electrode material has a higher compacted density, so that the battery has a higher battery capacity and better cycle performance. Too large compaction density can lead to too tight contact between material particles and enhanced electron conductivity, but the ion movement channel is reduced, polarization is increased in the discharge process, voltage is rapidly reduced, and capacity is reduced; the compaction density is too small, the distance between particles is large, the electrolyte is absorbed more, the movement of ions is facilitated, the contact area between particles is small, the electron conduction capacity is reduced, and the discharge electrode is increased.
In another embodiment of the present invention, the matrix has the chemical formula Li x2 Ni 1-a-b-z Co a Mn b N z O 2 When the positive electrode material is compacted, the density is 4-5 g/cm 3 . For example 4g/cm 3 、4.2g/cm 3 、4.4g/cm 3 、4.6g/cm 3 、4.8g/cm 3 、5g/cm 3 Any one of the values or a range between any two of the values. In this compacted density range, the positive electrode material has a higher compacted density, so that the battery has a higher battery capacity and better cycle performance. Too large compaction density can lead to too tight contact between material particles and enhanced electron conductivity, but the ion movement channel is reduced, polarization is increased in the discharge process, voltage is rapidly reduced, and capacity is reduced; the compaction density is too small, the distance between particles is large, the electrolyte is absorbed more, the ion movement is facilitated, the contact area between particles is small, the electron conduction capacity is reduced, and the electrode is dischargedThe degree of chemical amplification increases.
The invention also provides a preparation method of the positive electrode material, which comprises the following steps:
a) Preparing a matrix;
b) Mixing the matrix prepared in the step a) with a spinel structure compound, and performing first sintering to obtain a positive electrode material coated by a first coating layer;
c) Mixing the positive electrode material coated by the first coating layer prepared in the step b) with a fast ion conductor compound, and performing second sintering to obtain the final positive electrode material.
In an embodiment of the invention, the matrix has the chemical formula Li x1 Co 1-x-y Al x M y O 2 Or Li (lithium) x2 Ni 1-a-b- z Co a Mn b N z O 2 ，
In one embodiment of the invention, matrix Li x1 Co 1-x-y Al x M y O 2 The preparation method comprises the following steps:
(a11) Mixing soluble aluminum salt, soluble cobalt salt, solvent and complex precipitant, and performing coprecipitation reaction to obtain Al doped Co 3 O 4 A precursor;
(a12) Mixing the precursor prepared in the step (a 11), the oxide containing M element and a lithium source, and sintering for 8-16 h in an air atmosphere at 800-1100 ℃ to obtain a matrix material Li x1 Co 1-x-y Al x M y O 2 。
Preferably, the soluble aluminum salt and the soluble cobalt salt may be sulfate, carbonate, acetate, chloride, nitrate, or the like.
Preferably, the solvent is water and/or an organic solvent.
In embodiments provided herein, the solvent comprises any one or a combination of at least two of water, methanol, ethanol, acetone, propanol, isopropanol, ethylene glycol, n-butanol, cyclohexane, ethylenediamine, azamethylpyrrolidone, benzene, toluene, xylene, methyl ether, or diethyl ether.
Preferably, the complexing precipitant includes, but is not limited to, one or more of hydroxide, carbonate, oxalate, ammonia.
In the examples provided herein, the complexing precipitant is ammonia water and sodium carbonate.
Preferably, the oxide containing M element may be various forms of oxide or a mixture thereof.
In an embodiment provided by the invention, the lithium source comprises at least one of lithium carbonate, lithium nitrate, lithium hydroxide.
In a specific embodiment provided by the invention, the lithium source is lithium carbonate.
According to an embodiment of the invention, in step (a 11), the molar ratio of cobalt in the soluble cobalt salt to aluminum in the soluble aluminum salt, n (Co): n (Al) is 100: (3-5).
According to an embodiment of the present invention, in the step (a 11), the solvent is water, and the mass ratio of the soluble cobalt salt to the water is (500 to 700): 1500.
according to an embodiment of the present invention, in the step (a 11), the complexing precipitant includes ammonia water, the concentration of the ammonia water is 10% -15%, and the volume ratio of the ammonia water to the water is 2:1.
According to an embodiment of the present invention, in step (a 11), the coprecipitation reaction is performed under an inert atmosphere and stirring.
In a specific embodiment of the present invention, the inert atmosphere is nitrogen.
According to an embodiment of the present invention, in the step (a 11), the nitrogen is introduced and stirred at a flow rate of 20 to 40mL/min and a stirring speed of 650 to 850 rpm.
According to an embodiment of the present invention, in step (a 11), the pH of the coprecipitation reaction is 6 to 8, the reaction temperature is 50 to 65℃and the reaction time is 36 to 50 hours.
According to an embodiment of the present invention, in step (a 12), a lithium source, al-doped Co 3 O 4 N (Li) in the oxide containing M element: n (co+al): n (M) =1.0 to 1.08:1 (0.0005 to 0.01).
Preferably, the conditions for the first sintering are: the sintering environment is air atmosphere or oxygen atmosphere, the sintering temperature is 800-1000 ℃, and the sintering time is 5-10 h.
Preferably, the conditions of the first sintering or the second sintering are: the sintering environment is air atmosphere or oxygen atmosphere, the sintering temperature is 700-1000 ℃, and the sintering time is 4-10 h.
In another embodiment of the present invention, the matrix material Li x2 Ni 1-a-b-z Co a Mn b N z O 2 The preparation method comprises the following steps:
(a21) Mixing soluble nickel salt, soluble cobalt salt, soluble manganese salt, solvent and complex precipitant, and performing coprecipitation reaction to obtain Ni 1-a-b Co a Mn b (OH) 2 A precursor;
(a22) Mixing the precursor, a lithium source and an oxide containing N element, and sintering for 8-16 h in the air or oxygen atmosphere at 700-1000 ℃ to obtain a matrix material Li x2 Ni 1-a-b-z Co a Mn b N z O 2 。
Preferably, the soluble nickel salt, soluble cobalt salt, soluble manganese salt may be sulfate, carbonate, acetate, chloride, nitrate, etc.
Preferably, the solvent is water and/or an organic solvent.
In embodiments provided herein, the solvent comprises any one or a combination of at least two of water, methanol, ethanol, acetone, propanol, isopropanol, ethylene glycol, n-butanol, cyclohexane, ethylenediamine, azamethylpyrrolidone, benzene, toluene, xylene, methyl ether, or diethyl ether.
Preferably, the complexing precipitant includes, but is not limited to, one or more of hydroxide, carbonate, oxalate, ammonia.
In the examples provided herein, the complexing precipitant is ammonia and sodium hydroxide.
Preferably, the N-containing oxide may be various forms of oxide or a mixture thereof.
In an embodiment provided by the invention, the lithium source comprises at least one of lithium carbonate, lithium nitrate, lithium hydroxide.
In a specific embodiment provided herein, the lithium source is lithium hydroxide.
According to an embodiment of the present invention, in step (a 21), the molar ratio n (Ni) of nickel in the soluble nickel salt, cobalt in the soluble cobalt salt, manganese in the soluble manganese salt: n (Co): n (Mn) is (0.5 to 1): (0-1/3): (0-1/3).
According to an embodiment of the present invention, in step (a 21), the pH of the coprecipitation reaction is 10 to 12, the reaction temperature is 50 to 60℃and the reaction time is 24 to 48 hours.
According to an embodiment of the present invention, in the step (a 21), the complexing precipitant includes ammonia water, the concentration of the ammonia water is 10% -18%, and the volume ratio of the ammonia water to the water is 2:1.
According to an embodiment of the present invention, in step (a 21), the coprecipitation reaction is performed under an inert atmosphere and stirring.
In a specific embodiment of the present invention, the inert atmosphere is nitrogen.
According to an embodiment of the present invention, in step (a 22), the lithium source, ni 1-a-b Co a Mn b (OH) 2 N (Li) in the precursor and the N-containing oxide: n (ni+co+mn): n (N) = (1.0-1.05): 0.9-1): 0-0.1.
According to an embodiment of the present invention, the nano spinel structure compound AB 2-m C m O 4 Coating agent and nano lithium niobium tungsten oxide coating agent Li d Nb e W f O 6 Can be obtained by purchase or experimental preparation, and the preparation method is a common preparation method in the field.
The invention also provides a positive plate, which comprises the positive material.
Preferably, the positive plate has a compacted density of 3.2 to 4.5g/cm 3 。
In one embodiment of the invention, the matrix has the chemical formula Li x1 Co 1-x-y Al x M y O 2 When the positive plate is compacted, the density is 4.0-4.5 g/cm 3 。
In another embodiment of the inventionWherein the chemical general formula of the matrix is Li x2 Ni 1-a-b-z Co a Mn b N z O 2 When the positive plate is compacted, the density is 3.2-4.0 g/cm 3 。
In the above-mentioned compaction density range, it is shown that the positive electrode sheet has a higher compaction density, thereby improving the energy density of the battery.
According to an embodiment of the present invention, a positive electrode sheet includes a positive electrode current collector and a positive electrode active material layer coated on at least one side surface of the positive electrode current collector, the positive electrode active material layer including the above-described positive electrode material.
According to an embodiment of the present invention, the positive electrode active material layer further includes a conductive agent. In some embodiments, the conductive agent is selected from one or more of conductive carbon black, acetylene black, ketjen black, carbon fiber, graphene, single-walled carbon nanotubes, multi-walled carbon nanotubes.
According to an embodiment of the present invention, the positive electrode active material layer further includes a binder. In some embodiments, the binder is selected from one or more of carboxymethyl cellulose, sodium carboxymethyl cellulose, lithium carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyethylene, polyvinyl alcohol, polyvinyl chloride, polyvinyl fluoride, polyvinylpyrrolidone, polytetrafluoroethylene, polypropylene, styrene-butadiene rubber, epoxy resin, butadiene-based rubber binder, acrylonitrile-based binder.
According to an embodiment of the present invention, the positive electrode active material layer contains the following components in percentage by mass:
91-97.5 wt% of positive electrode material, 0.5-4 wt% of conductive agent and 2-5 wt% of binder.
The invention also provides a battery, which comprises the positive electrode material or the positive electrode plate.
Preferably, the battery is a lithium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
the invention combines lithium niobium tungsten oxide Li d Nb e W f O 6 As a coating layer, the surface of the positive electrode material can be optimized to reduce the impedance, therebyAnd the cycle stability and the thermal stability of the lithium ion battery are improved.
The invention is prepared by mixing spinel structure compound AB with high structure stability and thermal stability under high voltage 2-m C m O 4 A first coating layer as a matrix material, and a lithium-niobium-tungsten-oxygen compound Li d Nb e W f O 6 The spinel structure compound is used as a second coating layer, wherein the spinel structure compound is arranged on the surface of a matrix, so that the structure of the positive electrode material can be stabilized, and a gradient doping structure from the surface to a bulk phase can be formed on the surface of the matrix in the synthesis process, thereby improving the bulk phase structure stability of the positive electrode material; the fast ion conductor compound is arranged on the surface of the spinel structure compound, so that the surface of the positive electrode material can be further optimized, the impedance is reduced, and the cycle stability and the thermal stability of the lithium ion battery are improved.
Drawings
FIG. 1 is a schematic structural view of a positive electrode material in example 1;
FIG. 2 is a topography of the positive electrode material of example 1;
fig. 3 is a cross-sectional view of the positive electrode material in example 1.
Reference numerals:
1, a matrix; 2 a first cladding layer; and 3, a second coating layer.
Detailed Description
The invention discloses a positive electrode material, a positive electrode plate and a battery, and the technical parameters can be properly improved by a person skilled in the art by referring to the content of the invention. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and are deemed to be included in the present invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that variations and modifications can be made in the methods and applications described herein, and in the practice and application of the techniques of this invention, without departing from the spirit or scope of the invention.
Term interpretation:
spinel structure: in the crystal structure, oxygen ions are arranged in cubic close packing, and divalent cations are filled inIn one eighth of the tetrahedral voids, the trivalent cations are filled in one half of the octahedral voids. With magnesia-alumina spinel MgAl 2 O 4 As a representative representation: the spinel unit cell can be divided into 8 small cubic units, which are respectively pieced together by 4 small units of type A and 4 small units of type B. Each small unit of A type and B type has 4O 2- Ions, O in unit cell 2- Is 8*4 =32. Mg of 2+ At the center and half of the apexes of the A-type small units and half of the apexes of the B-type small units, mg in the unit cell 2+ The number of (2) is 4 (1+4/8) + 4*4/8. Mg of 2+ In four coordinates, i.e. occupying O 2- Tetrahedral voids in close packing. 4 Al in each B-type small unit 3+ Al in unit cell 3+ Is 4*4 =16. Al (Al) 3+ In six-coordinate form, i.e. occupying O 2- Octahedral voids in close packing.
Fast ion conductor (fast ionic conductor): also called super ionic conductor, solid electrolyte, which is distinguished from general ionic conductor by having ion conductivity (0.01Ω.cm) and low ion conductivity activation energy (.ltoreq.0.40 eV) in a certain temperature range compared with liquid electrolyte. Most fast ion conductors are inorganic compounds, and there are fast ion conductors in which at least the organic materials are silver, copper and hydrogen ions.
LiNbWO 6 Has two structures of tetragonal phase and hexagonal phase, wherein tetragonal system LiNbWO 6 Is P-421m, and the hexagonal system LiNbWO 6 Is R3c. The results of the crystal structure characterization show that: tetragonal LiNbWO 6 With wider transmission channels (O-O spacing in the duct
) Can be used for the intercalation and deintercalation of alkali ions; while hexagonal LiNbWO 6 The nearest distance between O and O in the transmission channel of (2) is +.>
Furthermore due to tetragonal LiNbWO 6 Surface energy (0.419J/m) 2 ) Low, which tends to form a thin (300 nm) thicknessRice) cake-like structure; while hexagonal LiNbWO 6 Has very high surface energy (6.074J/m) 2 ) This makes it easy to form a cubic-like microstructure with a thickness of about 5 microns.
The reagents, instruments, materials, etc. used in the present invention are commercially available.
The invention is further illustrated by the following examples:
example 1
1. Preparation of cathode Material
1) Co doped with Al element is synthesized by adopting coprecipitation method 3 O 4 Preparing the precursor, namely mixing aluminum sulfate and cobalt sulfate according to a molar ratio n (Al): n (Co) =3.5:96.5, dissolving the mixture into deionized water, and performing coprecipitation reaction in a reaction kettle to obtain Co doped with Al element 3 O 4 A precursor; the reaction temperature is 50 ℃, the reaction time is 36 hours, and ammonia water and sodium carbonate are introduced to adjust the pH of the reaction to 7.5; co doped with Al element 3 O 4 Precursor, lithium carbonate, mgO and La 2 O 3 In molar ratio n (Li): n (co+al): n (Mg): n (La) =1.05:1:0.004:0.0005, and sintering for 12h under the condition of 1050 ℃ in an air atmosphere to obtain a matrix material LiCo 0.9605 Al 0.035 Mg 0.004 La 0.0005 O 2 ；
2) LiCo as a matrix material in step 1) 0.9605 Al 0.035 Mg 0.004 La 0.0005 O 2 And spinel structure compound NiCo 1.995 W 0.005 O 4 According to the weight ratio of 1: mixing 0.5% evenly, sintering for 8 hours under the condition of 900 ℃ in air atmosphere to obtain spinel structure compound NiCo 1.995 W 0.005 O 4 A coated positive electrode material;
3) NiCo in step 2) is subjected to 1.995 W 0.005 O 4 Coated cathode material and LiNbWO 6 According to the weight ratio of 1: mixing 0.5% uniformly, sintering for 6h at 800 ℃ in air atmosphere to obtain the final spinel structure compound NiCo 1.995 W 0.005 O 4 And a fast ion conductor compound LiNWO 6 And (3) jointly coating the positive electrode material.
Fig. 2 and 3 show an overall morphology and a cross-sectional morphology, respectively, of the positive electrode material of the present embodiment.
2. And (3) assembling a button cell:
uniformly mixing the positive electrode material, the conductive agent and the binder PVDF according to the mass ratio of 95:2.5:2.5, and dispersing the mixture by using an N-methylpyrrolidone (NMP) solvent to form slurry; the slurry is uniformly coated on an aluminum foil sheet and dried for 12 hours at 80 ℃ to obtain a positive electrode sheet, and the dried positive electrode sheet is rolled and cut into a wafer and put into a glove box for standby. The wafer prepared above is used as positive electrode, metallic lithium is used as negative electrode, celgard 2400 (microporous polypropylene film) is used as diaphragm, and 1mol/L LiPF 6 + (EC: EMC: dmc=1:1:1) as electrolyte, a 2032 type button cell was assembled.
3. And (3) assembling a lithium ion battery:
(1) Preparation of positive plate
The positive electrode material, the binder, the conductive carbon black SP and the carbon nano tube CNT which are prepared by the method are mixed according to the weight ratio of 96:2:1.5:0.5, mixing, adding N-methyl pyrrolidone (NMP), stirring under the action of a vacuum stirrer to obtain a positive electrode slurry with uniform fluidity, and adding N-methyl pyrrolidone (NMP) in the process to adjust the solid content of the positive electrode slurry; uniformly coating the positive electrode slurry on aluminum foil with the model of 12 mu m, wherein the coating surface density is controlled to be 15.0mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the And baking the coated aluminum foil in 5 sections of baking ovens with different temperature gradients, rolling the baked pole piece twice, and slitting and ultra-welding the rolled pole piece to obtain the required positive pole piece.
(2) Preparation of negative plate
Graphite as a cathode active material, sodium carboxymethyl cellulose (CMC-Na) as a thickener, styrene butadiene rubber SBR as a binder and acetylene black SP as a conductive agent according to the weight ratio of 96.5:1.0:1.0:1.5, mixing, adding deionized water as a solvent, and obtaining negative electrode slurry under the action of a vacuum stirrer; uniformly coating the negative electrode slurry on a copper foil; and baking the coated copper foil in 3 sections of baking ovens with different temperature gradients, rolling the baked pole piece twice, and slitting and ultra-welding the rolled pole piece to obtain the required negative pole piece.
(3) Electrolyte preparation and separator preparation
The electrolyte adopts commercial electrolyte, and takes ethylene carbonate, propylene carbonate and diethyl carbonate as solvents according to the mass ratio of 1:1:1, and 1mol/L lithium hexafluorophosphate (LiPF 6 ) As lithium salt, film forming additive and high voltage additive are added into the components; the 7+3 mu m mixed coating diaphragm (substrate polypropylene film+PVDF)&Ceramic hybrid coating) as a barrier film.
(4) Preparation of lithium ion batteries
Sequentially stacking the prepared positive plate, the prepared isolating film and the prepared negative plate, and preparing a multi-lug type battery cell by switching a multi-layer aluminum foil of the positive electrode of the battery cell with an aluminum lug through an aluminum foil and switching a multi-layer copper foil of the negative electrode with a nickel lug through a copper foil; the two layers of isolating films wrap the negative electrode plate, the positive electrode plate is placed on the isolating film, the isolating film is ensured to be positioned between the positive electrode plate and the negative electrode plate to play a role in isolating and subsequently transmitting lithium ions, and then the bare cell without liquid injection is obtained through winding; and (3) heat-sealing the bare cell in a shell made of an aluminum plastic film, injecting electrolyte into the bare cell with the baked moisture value less than 200ppm, and performing the procedures of vacuum packaging, hot and cold molding, formation, shaping, sorting and the like to obtain the lithium ion battery.
Example 2
The preparation method of reference example 1 is different only in that the spinel-structured compound in the positive electrode material preparation step 2) is NiCo 1.995 Ti 0.005 O 4 。
Example 3
The preparation method of reference example 1 is different only in that the mass ratio of the fast ion conductor compound in the positive electrode material preparation step 3) is 0.75%.
Example 4
The preparation method of reference example 1 differs only in the positive electrode material preparation step 1), specifically as follows:
co doped with Al element is synthesized by adopting coprecipitation method 3 O 4 Preparing the precursor, namely mixing aluminum sulfate and cobalt sulfate according to a molar ratio n (Al): n (Co) =3.5:96.5, dissolving the mixture into deionized water, and performing coprecipitation reaction in a reaction kettle to obtain Co doped with Al element 3 O 4 A precursor; the reaction temperature is 50 ℃, the reaction time is 36 hours, and ammonia water and sodium carbonate are introduced to adjust the pH of the reaction to 7.5; co doped with Al element 3 O 4 Precursors, lithium carbonate, mgO and ZrO 2 Mixing n (Li) n (Co+Al) n (Mg) n (Zr) =1.05:1:0.004:0.0005, and sintering at 1050 deg.C in air atmosphere for 12 hr to obtain LiCo as matrix material 0.9605 Al 0.035 Mg 0.004 Zr 0.0005 O 2 The remainder was referred to the preparation procedure of example 1.
Example 5
The preparation method of reference example 1 was different only in that the content of the spinel-structured compound in the positive electrode material preparation step 2) was 0.02%.
Example 6
The preparation method of reference example 1 was different only in that the content of the spinel-structured compound in the positive electrode material preparation step 2) was 1%.
Example 7
The preparation method of reference example 1 differs only in the positive electrode material preparation step 1), specifically as follows:
mixing nickel sulfate, cobalt sulfate and manganese sulfate according to the molar ratio of n (Ni): n (Co): n (Mn) =8:1:1, dissolving in deionized water, and performing coprecipitation reaction in a reaction kettle to obtain Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 The method comprises the steps of carrying out a first treatment on the surface of the Ammonia water and sodium hydroxide are introduced to adjust the pH of the reaction to 11, the reaction temperature is 55 ℃, and the reaction time is 48 hours under the nitrogen atmosphere; ni is added with 0.8 Co 0.1 Mn 0.1 (OH) 2 Lithium hydroxide, zrO 2 And WO 3 Mixing n (Li) n (Ni+Co+Mn) n (Zr) n (W) =1.05:1:0.002:0.001, and sintering at 800 deg.C in oxygen atmosphere for 12 hr to obtain matrix material LiNi 0.8 Co 0.097 Mn 0.1 Zr 0.002 W 0.001 O 2 The remainder was referred to the preparation procedure of example 1.
Example 8
The preparation method of reference example 1 differs only in the positive electrode material preparation step 1), specifically as follows:
mixing nickel sulfate and manganese sulfate according to a molar ratio of n (Ni): n (Mn) =7.5:2.5, dissolving in deionized water, and performing coprecipitation reaction in a reaction kettle to obtain Ni 0.75 Mn 0.25 (OH) 2 The method comprises the steps of carrying out a first treatment on the surface of the Ammonia water and sodium hydroxide are introduced to adjust the pH of the reaction to 11, the reaction temperature is 55 ℃, and the reaction time is 48 hours under the nitrogen atmosphere; ni is added with 0.75 Mn 0.25 (OH) 2 Lithium hydroxide, al 2 O 3 And ZrO(s) 3 Mixing n (Li) n (Ni+Mn) n (Al) n (Zr) =1.05:1:0.006:0.002, and sintering at 850 deg.C in oxygen atmosphere for 12 hr to obtain matrix material LiNi 0.75 Mn 0.242 Al 0.006 Zr 0.002 O 2 The remainder was referred to the preparation procedure of example 1.
Example 9
The preparation method of reference example 1 is different only in that the step 2) of coating the spinel-structured compound is not performed in the preparation process of the cathode material.
Comparative example 1
The preparation method of reference example 1 is different only in that there is no coating of the spinel-structured compound of step 2) and the fast ion conductor compound of step 3) in the preparation process of the positive electrode material.
Comparative example 2
The preparation method of reference example 1 is different only in that the coating of the fast ion conductor compound of step 3) is not performed in the preparation process of the positive electrode material.
Comparative example 3
The preparation method of reference example 8 is different only in that the step 2) coating of the spinel-structured compound and the step 3) coating of the fast ion conductor compound are not performed in the preparation process of the positive electrode material.
Comparative example 4
The preparation method of reference example 8 is different only in that the step 2) coating of the spinel-structured compound is not performed in the preparation process of the cathode material.
Comparative example 5
The preparation method of reference example 8 is different only in that the coating of the fast ion conductor compound of step 3) is not performed in the preparation process of the positive electrode material.
Table 1 characteristic parameters of examples and comparative examples
Test case
a) Discharge gram Capacity and multiplying power test
The prepared button cell is tested at the temperature of 25 ℃ under the condition of 3.0-4.6V in a voltage interval, wherein the charging multiplying power is 0.1C, and the discharging multiplying power is 0.1C, 0.2C, 0.5C, 1C and 2C in sequence.
b) Cycle capacity test
Placing the battery cell in an environment of 25+/-2 ℃ (45+/-2 ℃);
1) Discharging 0.7C to lower limit voltage (3.0V), and standing for 10min;
2) Charging 2C to upper limit voltage (4.5V), stopping 0.05C, and standing for 10min;
3) Discharging the 2C to a lower limit voltage (3.0V), and standing for 10min;
4) Charging 2C to upper limit voltage (4.5V), stopping 0.05C, and standing for 10min; repeating the 3-4 steps for 1000 times.
Capacity retention formula: the first cycle test capacity is designated as A1, and after 800 cycles the test capacity is designated as A2; capacity retention = A2/a1×100%.
The specific test results are shown in Table 2.
Table 2 battery performance of examples and comparative examples
From the specific test results of examples and comparative examples in table 2, it can be seen that the batteries employing the embodiments of the present invention exhibited excellent electrochemical performance in gram capacity, rate capability and cycle performance at high voltages of 3.0 to 4.6V, whereas the batteries of the comparative examples were inferior to the electrochemical performance of the batteries of the examples in gram capacity, rate capability and cycle performance.
In comparison with comparative example 1, example 9 is coated with a fast ion conductor compound LiNWO 6 The rate performance is improved to a certain extent compared with that of comparative example 1, and the capacity is also improved, mainly because of the fast ion conductor compound LiNWO 6 The diffusion performance of lithium ions is improved, the dynamic performance of the battery is improved, an additional Li source can be provided, and a certain Li supplementing effect is achieved.
The differences between example 1 and comparative examples 1-2 are mainly that: comparative example 1 does not coat any substance, so the electrochemical performance as a whole is poor; the compound with the spinel structure is coated in the comparative example 2, so that the bulk phase and structural stability of the positive electrode material are improved; and the effect of coating the spinel structure compound and the fast ion conductor compound together is good, so that the coordination effect is achieved, and the performance of the battery is enhanced.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A positive electrode material, characterized in that the positive electrode material comprises a substrate and a coating layer; the coating layer comprises a compound containing Li, nb and W elements.
2. The positive electrode material according to claim 1, wherein the compound containing Li, nb, W elements includes Li d Nb e W f O 6 ，
Wherein d is more than 0.95 and less than 1.05,0.95, e is more than 1.05,0.95 and f is more than 1.05;
preferably, the Li, nb and W element-containing compound is LiNbWO 6 ；
Preferably, the mass content of the compound containing Li, nb and W elements in the positive electrode material is 0.02-1%;
preferably, the thickness of the coating layer is 10-50 nm.
3. The positive electrode material according to claim 1, wherein the coating layer further comprises a spinel structure compound;
preferably, the spinel structure compound has the chemical formula AB 2-m C m O 4 ，
Wherein m is more than or equal to 0 and less than 0.01, A and B are respectively and independently selected from one of Al, mg, ti, co, ni, A and B are different, and C is selected from at least one of Al, mg, ti, W, nb, mo, te, ce;
preferably, the spinel structure compound is 0.02% -1% by mass in the positive electrode material.
4. The positive electrode material according to claim 3, wherein the coating layer is one coating layer or two coating layers;
preferably, the coating layer is a two-layer coating layer, the coating layer comprising spinel structure compound is a first coating layer, the coating layer comprising Li, nb and W element compounds is a second coating layer, the first coating layer is arranged on the surface of the substrate, and the second coating layer is arranged on the surface of the substrate coated with the first coating layer.
5. The positive electrode material according to claim 4, wherein the thickness of the first coating layer is 5 to 30nm;
and/or the thickness of the second coating layer is 5-30 nm;
and/or the sum of the thicknesses of the first coating layer and the second coating layer is 10-50 nm.
6. The positive electrode material according to claim 1, wherein the base is doped with an a element and a B element, each of a and B is independently selected from one of Al, mg, ti, co, ni, and a and B are different;
the element A and the element B are in a gradient doping state in the matrix;
preferably, the gradient doping is such that the bulk content gradually decreases from the surface.
7. The positive electrode material according to any one of claims 1 to 6, wherein the matrix comprises one or more of a transition metal lithium oxide, lithium iron phosphate, lithium manganese iron phosphate, lithium-rich manganese-based material;
preferably, the matrix has the chemical formula Li x1 Co 1-x-y Al x M y O 2 And/or Li x2 Ni 1-a-b-z Co a R b N z O 2 ，
Wherein x is more than 0.95 and less than or equal to 1 and less than or equal to 1.05,0.03 and less than or equal to 0.05 or x= 0,0.0005 and less than or equal to y and less than or equal to 0.01, and M comprises at least one of Mg, mn, ni, ti, la, Y, zr, W, nb, te, ce; r comprises Mn and/or Al;
x2 is more than 0.95 and less than 1.05,0, a is more than or equal to 1/3, b is more than or equal to 0 and less than or equal to 1/3, z is more than or equal to 0 and less than or equal to 0.01, and N is at least one of Mn, al, mg, ti, zr, W, nb, B, la, Y, mo, si;
preferably, 0.ltoreq.a+b.ltoreq.0.5.
8. The positive electrode material according to claim 1, wherein the positive electrode material has a particle diameter D50 of 3 to 20 μm; and/or the positive electrode material has a compacted density of 3.5-5 g/cm 3 ；
And/or the chemical general formula of the matrix is Li x1 Co 1-x-y Al x M y O 2 When the particle diameter D50 of the positive electrode material is 10-20 mu m; and/or the positive electrode material has a compacted density of 3.5-4.5 g/cm 3 ；
And/or the chemical general formula of the matrix is Li x2 Ni 1-a-b-z Co a Mn b N z O 2 When the particle diameter D50 of the positive electrode material is 3-15 mu m; and/or the positive electrode material has a compacted density of 4-5 g/cm 3 。
9. A positive electrode sheet, characterized in that the positive electrode sheet comprises the positive electrode material according to any one of claims 1 to 8;
preferably, the positive electrode sheet has a compacted density of 3.2 to 4.5g/cm 3 ；
Preferably, the matrix has the chemical formula Li x1 Co 1-x-y Al x M y O 2 When the positive plate is in a compact density of 4.0-4.5 g/cm 3 ；
Preferably, the matrix has the chemical formula Li x2 Ni 1-a-b-z Co a Mn b N z O 2 When the positive plate is in a compact density of 3.2-4.0 g/cm 3 。
10. A battery comprising the positive electrode material according to any one of claims 1 to 8, and/or the positive electrode sheet according to claim 9.
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