CN113363483A - Olivine-structure positive electrode material, preparation method and application thereof, and lithium ion battery - Google Patents
Olivine-structure positive electrode material, preparation method and application thereof, and lithium ion battery Download PDFInfo
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Abstract
The invention relates to the field of lithium ion batteries, and discloses an olivine-structure positive electrode material, a preparation method and application thereof, and a lithium ion battery. The anode material comprises a substrate and a coating layer coated on the surface of the substrate; the matrix has a composition represented by formula I: li1+a[(Fe1‑ xMnx)1‑bMy]PO4Formula I; a is more than or equal to 0.5 and less than or equal to 0.3, b is more than or equal to 0 and less than or equal to 0.4, x is more than or equal to 0 and less than or equal to 1, 0<y is less than or equal to 0.04; the coating layer is graphitized porous carbon and has a composition shown in a formula II: CD (compact disc)vFormula II; v is more than or equal to 0 and less than or equal to 0.4. The cathode material has excellent lithium ion mobility, electrochemical performance and cycle performance in the charge-discharge process, and has excellent ion conductivity compared with the traditional carbon-coated olivine structure cathode material,the positive electrode material is used for the lithium ion battery, and can obviously improve the capacity, the multiplying power and the cycle performance of the lithium ion battery.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to an olivine structure positive electrode material, a preparation method and application thereof, and a lithium ion battery.
Background
With the rapid development of electric automobiles and energy storage markets, in recent years, people have made higher requirements on the energy density, cycle life and safety performance of the existing lithium ion batteries and the anode materials thereof. In which differentiated performance requirements are placed on different application scenarios. For the markets of energy storage and commercial vehicle power batteries which require high safety performance, long cycle life and low cost, the olivine structure anode material represented by lithium iron phosphate has stronger competitive advantages.
Compared with the layered multi-component material, the olivine type anode material is stable (PO) with P due to the fact that all oxygen ions in the crystal structure of the olivine type anode material are formed by strong covalent bonds4)3-The tetrahedral structure ensures that oxygen in crystal lattices is not easy to lose, and oxygen generated by decomposition due to deep deintercalation of lithium is not generated, so that the material has the advantages of high safety performance, long cycle life, low cost and the like. But this olivine-type crystal structure also limits the electron conductivity and the lithium ion diffusion rate. Therefore, it needs to be modified by doping, cladding, and the like. In the prior art, organic matters such as sucrose and glucose are generally used as carbon sources to coat the olivine-structured positive electrode material, so that the electronic conductivity of the positive electrode material is improved, and the primary particle size of the positive electrode material is inhibited. However, it is difficult to obtain a uniform and complete carbon coating, which results in low carbon content and high resistivity in some regions, and increases the overall internal resistance of the material, thereby affecting the electrochemical performance of the material.
CN102185140A discloses a method for preparing a nano-network conductive polymer coated lithium iron phosphate cathode material, which is characterized in that a surfactant is used as a template, and a conductive polymer monomer is polymerized in situ on the surface of lithium iron phosphate in a low-temperature acidic solution medium and grows into a nano-network structure, so as to form the nano-network conductive polymer coated lithium iron phosphate cathode material. The special morphology of the nano-network conductive polymer is beneficial to the conduction of carriers among polymer aggregate particles, has high carrier mobility, and can form an effective conductive network by coating the nano-network conductive polymer on the surface of lithium iron phosphate, so that the conductivity of the lithium iron phosphate is improved, and the electrochemical performance of the electrode material is improved. However, the process needs to carry out secondary coating on the finished lithium iron phosphate cathode material, needs to use a strong oxidant to initiate polymerization reaction, is complex in process and high in cost, also puts higher requirements on production safety and environmental protection, and is not beneficial to large-scale industrial application.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide an olivine-structure positive electrode material, a preparation method and application thereof, and a lithium ion battery. The olivine-structure positive electrode material comprises a substrate and a coating layer coated on the surface of the substrate, so that the positive electrode material has excellent lithium ion mobility, electrochemical performance and cycle performance in the charging and discharging processes, and compared with the traditional carbon-coated positive electrode material, the positive electrode material has excellent ion conductivity, and when the positive electrode material is used for a lithium ion battery, the capacity, multiplying power and cycle performance of the lithium ion battery can be remarkably improved.
In order to achieve the above object, a first aspect of the present invention provides an olivine-structured positive electrode material, including a base and a coating layer coated on a surface of the base;
the matrix has a composition represented by formula I:
Li1+a[(Fe1-xMnx)1-bMy]PO4formula I
Wherein M is at least one selected from La, Cr, Mo, Ca, Hf, Ti, Mn, Fe, Zn, Y, Zr, W, Nb, Sm, Co, Ni, V, Mg, Na, B and Al; a is more than or equal to 0.5 and less than or equal to 0.3, b is more than or equal to 0 and less than or equal to 0.4, x is more than or equal to 0 and less than or equal to 1, and y is more than 0 and less than or equal to 0.04;
the coating layer is graphitized porous carbon and has a composition represented by formula II:
CDvformula II
Wherein D is selected from at least one of N, P, Si, S, B, F and Cl; v is more than or equal to 0 and less than or equal to 0.4.
The invention provides a preparation method of an olivine-structure positive electrode material, which is characterized by comprising the following steps of:
(1) mixing a lithium source, a precursor, a carbon source and a liquid medium, grinding the mixture to prepare slurry, and performing spray drying granulation to obtain a spray-dried material;
(2) calcining the spray-dried material in an inert atmosphere to obtain a sintered material;
(3) optionally crushing and screening the sintered material to obtain an olivine-structured positive electrode material;
wherein the method further comprises adding a metal source M, an organic ligand in step (1);
and/or, before the step (2), mixing the spray-dried material with the metal-organic framework material to obtain a mixed material.
The third aspect of the present invention provides an olivine-structured positive electrode material obtained by the above production method.
The fourth aspect of the invention provides an application of the olivine-structure cathode material in a lithium ion battery.
In a fifth aspect of the present invention, a lithium ion battery is provided, wherein the positive electrode material of the lithium ion battery is the above-mentioned olivine-structured positive electrode material.
Through the technical scheme, the olivine structure cathode material, the preparation method and the application thereof, and the lithium ion battery have the following beneficial effects:
(1) the olivine-structure positive electrode material provided by the invention has the advantages of good lithium ion mobility, excellent electrochemical performance and excellent cycle performance in the charge and discharge processes.
(2) According to the olivine-structure cathode material obtained by the invention, the surface of the substrate is coated with graphitized porous carbon with specific composition, the porosity of the metal organic framework material coating layer generated in situ in the material preparation process is inherited, and the ion conductivity of the olivine-structure cathode material is favorably improved compared with the traditional carbon coating.
(3) The olivine-structure cathode material provided by the invention is suitable for lithium ion batteries, a lithium ion transmission channel can be effectively constructed on the surface of the cathode material through a graphitized porous carbon coating layer generated by the induction of a coating metal organic framework material, so that the ionic conductivity of the cathode material is improved, meanwhile, the electronic conductivity is in the same level as that of common carbon coating, and the capacity, multiplying power and cycle performance of the battery are obviously improved.
(4) In the preparation method provided by the invention, a precursor of the nano-scale olivine-structured positive electrode material is formed in a liquid medium through grinding, and a uniformly-coated metal organic framework material coating layer is generated on the surface of the precursor in situ by the added metal salt and organic ligand through the dispersion effect of the liquid medium and the spray drying method.
(5) In the preparation method provided by the invention, the metal source containing the target doping element and the organic ligand are adopted, so that the doping element can be uniformly distributed in the matrix and the coating layer of the anode material by virtue of the process of generating the coating layer of the metal-organic framework material by the metal source and the organic ligand.
(6) The preparation method has simple process, does not need to greatly change the current mainstream process, does not need to additionally synthesize or purchase the finished metal organic framework material, directly synthesizes in situ in one step and has no pollution; the introduction mode of the doping elements and the coating materials is simple, the dosage can be less, and the method is suitable for industrial production.
Drawings
Fig. 1 is a scanning electron microscope photograph of a positive electrode material D1 of comparative example 1;
fig. 2 is a scanning electron microscope photograph of the olivine-structured positive electrode material C1 of example 1;
fig. 3 is a charge and discharge graph of the positive electrode materials of comparative example 1 and example 1 at 0.1C;
fig. 4 is a graph of discharge specific capacity of the positive electrode materials of comparative example 1 and example 1 at different rates;
fig. 5 is a raman spectrum of the positive electrode materials of example 1 and comparative example 1.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides an olivine-structure positive electrode material, which is characterized by comprising a substrate and a coating layer coated on the surface of the substrate;
the matrix has a composition represented by formula I:
Li1+a[(Fe1-xMnx)1-bMy]PO4formula I
Wherein M is at least one selected from La, Cr, Mo, Ca, Hf, Ti, Mn, Fe, Zn, Y, Zr, W, Nb, Sm, Co, Ni, V, Mg, Na, B and Al; a is more than or equal to 0.5 and less than or equal to 0.3, b is more than or equal to 0 and less than or equal to 0.4, x is more than or equal to 0 and less than or equal to 1, and y is more than 0 and less than or equal to 0.04;
the coating layer is graphitized porous carbon and has a composition represented by formula II:
CDvformula II
Wherein D is selected from at least one of N, P, Si, S, B, F and Cl; v is more than or equal to 0 and less than or equal to 0.4.
In the olivine-structure cathode material, the surface of a substrate is coated by a coating layer with a composition shown in formula II, the coating layer has a graphitized porous carbon structure (hereinafter referred to as GPC), and the porous structure of the coating layer can effectively construct a lithium ion transmission channel on the surface of the cathode material, so that the ion conductivity of the cathode material is remarkably improved.
Further, in the olivine-structure cathode material, the matrix with the composition shown in formula I is obtained by doping the matrix of the cathode material, so that the cathode material has excellent lithium ion mobility, electrochemical performance and cycle performance.
According to the present invention, when M is selected from at least one of Hf, Zr, Mg, Al, Ti, V, Mo, Ni, Co, Nb, and Na, the cathode material has more excellent lithium ion mobility, electrochemical properties, and cycle properties.
According to the present invention, when D is selected from at least one of N, P, Si, S, B, F, and Cl, the ion conductivity of the positive electrode material is further improved.
Further, when v is 0. ltoreq. v.ltoreq.0.2 in formula II, the ion conductivity of the positive electrode material is further improved.
In the invention, when the content of the coating layer in the cathode material is relatively less, the aim of improving the ion conductivity of the cathode material can be achieved. In order to make the positive electrode material have excellent lithium ion mobility, electrochemical performance and cycle performance, the content of the coating layer is 0.01-5 wt%, preferably 0.5-2.5 wt%, based on the total weight of the positive electrode material.
In the invention, the matrix in the olivine-structure cathode material has larger particle size, and the coating layer is uniformly coated on the surface of the matrix with thinner thickness. Preferably, the average particle diameter D of the positive electrode particles50Is 0.05-5 μm, and the average thickness of the coating layer is 1-100 nm.
In the invention, the coating layer has a porous structure, and compared with the traditional carbon coating material, the coating layer with the porous structure provided by the invention is more beneficial to improving the ionic conductivity of the cathode material.
According to the invention, the porosity of the coating is 10 to 200%, preferably 20 to 100%.
In the invention, the porosity of the coating layer is measured by a nitrogen adsorption method.
The invention provides a preparation method of an olivine-structure positive electrode material, which is characterized by comprising the following steps of:
(1) mixing a lithium source, a precursor, a carbon source and a liquid medium, grinding the mixture to prepare slurry, and performing spray drying granulation to obtain a spray-dried material;
(2) calcining the spray-dried material in an inert atmosphere to obtain a sintered material;
(3) optionally crushing and screening the sintered material to obtain an olivine-structured positive electrode material;
wherein the method further comprises adding a metal source M, an organic ligand in step (1);
and/or, before the step (2), mixing the spray-dried material with the metal-organic framework material to obtain a mixed material.
In the preparation method provided by the invention, the metal source containing the target doping element and the organic ligand are adopted, so that the doping element can be uniformly distributed in the matrix and the coating layer of the anode material by virtue of the process of generating the coating layer of the metal-organic framework material by the metal source and the organic ligand.
In the preparation method, before grinding, a metal source, an organic ligand, a lithium source and the like are added and mixed with a liquid medium at the same time, grinding is carried out to prepare slurry, and spray drying granulation is carried out to obtain a spray drying material; and/or mixing the metal organic framework material (formed by the reaction of a metal source and an organic ligand) with the spray-dried material to obtain a mixture, and then continuing to perform calcination treatment.
In the present invention, it is preferable that the metal source and the organic ligand are mixed with other raw materials and a liquid medium before the milling.
In the invention, a precursor of the nano-scale olivine-structured positive electrode material is formed in a liquid medium by grinding, a metal source and an organic ligand which are added are enabled to generate a uniformly coated metal organic framework material in situ on the surface of the precursor by means of the dispersion effect of the liquid medium and a spray drying method, and a carbon source is induced to form the coating layer by in situ roasting.
Furthermore, the preparation method of the invention has simple process, does not need to greatly change the current mainstream process, does not need to additionally synthesize or purchase the finished metal organic framework material, directly synthesizes in situ in one step and has no pollution; the introduction mode of the doping elements and the coating materials is simple, the dosage can be less, and the method is suitable for industrial production.
According to the present invention, the lithium source is at least one selected from the group consisting of lithium oxide, lithium hydroxide, lithium chloride, lithium nitrate, lithium nitrite, lithium formate, lithium acetate, lithium oxalate, lithium carbonate, lithium phosphate, dilithium hydrogen phosphate and lithium dihydrogen phosphate.
According to the invention, the precursor is selected from at least one of ferric phosphate, ferrous ammonium phosphate, ferrous manganese hydrogen phosphate and manganese hydrogen phosphate; or the precursor is selected from at least one of ferrous oxalate, ferrous manganese oxalate and a mixture selected from phosphoric acid and/or ammonium dihydrogen phosphate.
In the present invention, the precursor can provide Mn, Fe and PO in the matrix having the composition shown in formula I4。
According to the invention, the metal source M is selected from at least one of the nitrates, hydrochlorides, sulfates, acetates, metal oxides, metal oxychlorides, metal hydroxides, carbonates, phosphates, metal clusters, metal complexes and metal carboxylates capable of providing the element M.
According to the present invention, the carbon source is at least one selected from glucose, sucrose, fructose, cellulose, starch, citric acid, polyacrylic acid, phenol resin, polyethylene glycol, dopamine, graphene, and carbon nanotubes.
According to the invention, the organic ligand is selected from at least one of polycarboxyl organic acid, imidazole compounds, pyridine compounds and pyrimidine compounds.
In the present invention, the carbon source and the organic ligand can provide C and D in the coating layer having a composition represented by formula II.
In the present invention, examples of the imidazole-based compound include imidazole, 2-methylimidazole, 2-formylimidazole, 4-nitroimidazole, benzimidazole, and the like; examples of the pyridine compounds include pyridine, 2-aminopyridine, 4-ethylpyridine, 4-carboxypyridine and 3-pyridylpropanol; examples of the pyrimidine compound include pyrimidine, 5-carboxypyrimidine, and 2-amino-4-carboxypyrimidine; examples of the polycarboxy organic acid include fumaric acid, citric acid, succinic acid, dodecanedioic acid, terephthalic acid, trimesic acid, pyromellitic acid, terephthallic acid, naphthalenedicarboxylic acid, and porphyrinic acid.
In the present invention, the carbon source and the organic ligand may be partially or completely the same.
In the present invention, when the organic ligand is a polycarboxy organic acid, the method further comprises: in step (1), an alkali soluble cosolvent is added.
Preferably, the alkali soluble co-solvent is added simultaneously with the polycarboxy organic acid.
In the present invention, the basic co-solvent is selected from inorganic bases and/or organic amines. The inorganic base includes, but is not limited to, at least one of ammonia, sodium hydroxide, sodium carbonate, lithium hydroxide, lithium carbonate, and potassium hydroxide; the organic amine includes, but is not limited to, at least one of Triethylamine (TEA), triethanolamine, N-Dimethylformamide (DMF), N-Diethylformamide (DEF), N-2-methylpyrrolidone (NMP).
According to the invention, the liquid medium is selected from at least one of water, methanol, ethanol, propanol, ethylene glycol, isopropanol, benzyl alcohol, acetone, benzene, toluene, methyl ether, diethyl ether, acetic acid, xylene, tetrahydrofuran, dimethyl carbonate, N-methylpyrrolidone, propylene carbonate, triethylamine, triethanolamine, N-dimethylformamide, N-diethylformamide, acetonitrile and ethylene glycol dimethyl ether.
According to the invention, the adding molar ratio of the lithium source, the precursor, the carbon source, the metal source M and the organic ligand is (1-1.1): (0.96-1.04): (0.25-1):(0-0.04):(0-0.04).
In the present invention, the milling is carried out in a conventional ball milling apparatus, such as at least one of a planetary ball mill, a stirring mill and a sand mill.
According to the invention, in step (1), the grinding conditions comprise: ball-milling for 1-24h at the rotation speed of 100-600rpm by adopting a planetary ball mill; and/or, adopting a stirring mill and/or a sand mill to perform ball milling for 0.5-10h at the rotating speed of 300-3000 rpm.
According to the invention, in step (1), the solid content of the slurry is 10 to 70 wt%, and the particle size D of the slurry is50Is 50-5000 nm.
Further, the solid content of the slurry is 20-60 wt%, and the particle size D of the slurry is50Is 50-1000nm。
According to the present invention, in step (1), the spray-drying conditions include: the air inlet temperature is 180 ℃ and 280 ℃, and the air outlet temperature is 70-140 ℃.
According to the invention, the conditions of the calcination include: the calcination temperature is 500-900 ℃, preferably 600-800 ℃; the calcination time is 4-20h, preferably 6-15 h.
In the present invention, the inert gas is selected from nitrogen and/or argon.
In the present invention, the pulverization is jet milling.
The invention provides an olivine-structured positive electrode material prepared by the preparation method.
According to the invention, the anode material comprises a substrate and a coating layer coated on the surface of the substrate;
the matrix has a composition represented by formula I:
Li1+a[(Fe1-xMnx)1-bMy]PO4formula I
Wherein M is at least one selected from La, Cr, Mo, Ca, Hf, Ti, Mn, Fe, Zn, Y, Zr, W, Nb, Sm, Co, Ni, V, Mg, Na, B and Al; a is more than or equal to 0.5 and less than or equal to 0.3, b is more than or equal to 0 and less than or equal to 0.4, x is more than or equal to 0 and less than or equal to 1, and y is more than 0 and less than or equal to 0.04;
the coating layer is graphitized porous carbon and has a composition represented by formula II:
CDvformula II
Wherein D is selected from at least one of N, P, Si, S, B, F and Cl; v is more than or equal to 0 and less than or equal to 0.4.
The fourth aspect of the invention provides an application of the olivine-structure cathode material in a lithium ion battery.
In a fifth aspect of the present invention, a lithium ion battery is provided, wherein the positive electrode material of the lithium ion battery is the above-mentioned olivine-structured positive electrode material.
In a specific embodiment of the present invention, the lithium ion battery is a liquid lithium ion battery.
The present invention will be described in detail below by way of examples.
In the following examples of the present invention,
the average particle size of the anode material is measured by a laser particle sizer;
the thickness of the clad layer was measured by Transmission Electron Microscopy (TEM);
the apparent appearance of the cathode material is measured by a Scanning Electron Microscope (SEM);
the nano powder of the metal organic framework material UiO-66 is generated by the coordination of Zr and terephthalic acid, and the CAS number: 1072413-89-8, commercially available;
the other raw materials used in the examples and comparative examples of the present invention are all commercially available products.
Preparation example
The preparation method of the lithium ion battery comprises the following steps: and assembling the anode material D1 sample into a liquid lithium ion battery for electrochemical characterization. The method comprises the following specific steps:
mixing a positive electrode material D1, a conductive agent DB and polyvinylidene fluoride (PVDF) according to the mass ratio of 90: 5, coating the mixture on an aluminum foil, drying the aluminum foil, performing punch forming by using the pressure of 100MPa to form a positive electrode piece with the diameter of 12mm and the thickness of 120 mu m, and then putting the positive electrode piece into a vacuum drying oven to be dried for 12 hours at the temperature of 120 ℃. The negative electrode uses a Li metal sheet with the diameter of 17mm and the thickness of 1 mm; the diaphragm uses a polyethylene porous membrane with the surface coated with an alumina ceramic layer and the thickness of 25 μm; LiPF of 1.1mol/L is used as the electrolyte6The solvent is Ethylene Carbonate (EC), dimethyl carbonate (DMC) and Ethyl Methyl Carbonate (EMC) in a volume ratio of 1: 1: 1 (1.5 wt% of vinylene carbonate VC was added).
And assembling the positive pole piece, the diaphragm, the negative pole piece and the electrolyte into the 2025 type button cell in an Ar gas glove box with the water content and the oxygen content of less than 5 ppm.
Comparative example 1
Preparing a positive electrode material:
(1) lithium carbonate, iron phosphate (Fe/P ═ 0.97:1), sucrose and water were mixed, and then ground in a sand mill to obtain a slurry. The rotational speed of the sand mill is 1000rpm, and the time is 8 h. Wherein the adding molar ratio of lithium carbonate (calculated by Li), iron phosphate and sucrose (calculated by C) is 1.02:1: 0.3. Drying the obtained slurry by a spray dryerGranulating to obtain spray-dried material. The solid content of the slurry was 40 wt%, the particle size D of the slurry50Is 500 nm. The conditions of spray drying were: the air inlet temperature is 220 ℃, and the air outlet temperature is 100 ℃.
(2) And calcining the spray-dried material at 700 ℃ for 12h under the nitrogen protection atmosphere to obtain a sintered material.
(3) The sintering material is crushed by airflow and screened to obtain a matrix Li1.02Fe0.97PO4The coating layer is the positive electrode material LiFe of the common carbon coating layer0.97PO4and/C, recorded as D1. Average particle diameter D of D1501.8 μm, the thickness of the coating layer was about 10nm, the content of the coating layer was 1.31 wt%, and the porosity was 15%.
As shown in fig. 1, a scanning electron microscope image of the cathode material D1 is shown in fig. 1, and it can be seen from fig. 1 that the single-crystal lithium iron phosphate cathode material prepared in comparative example 1 has a non-uniform coating layer distribution.
The obtained positive electrode material is assembled into a liquid lithium ion button cell battery D1 according to the method of the preparation example, and electrochemical characterization is carried out.
The capacity and the cycle performance of the positive electrode material of the button cell battery D1 were examined 80 times by conducting charge-discharge cycles at 3.9-2.5V, 1C25 ℃ and 0.1C25 ℃. The results are shown in table 1, the button cell battery D1 assembled by the positive electrode material D1 has the specific discharge capacity of 159.8mAh/g at 0.1C25 ℃ and 96.7% of coulombic efficiency at 0.1C25 ℃ under the conditions of 3.9-2.5V and 0.1C25 ℃, the specific first-cycle discharge capacity of 143.9mAh/g at 1C25 ℃ and the capacity retention rate of 99% after 80-week circulation.
The charge and discharge curve of the button cell D1 at 0.1C is shown in figure 3, and the discharge specific capacity curve of the button cell D1 at different multiplying power is shown in figure 4.
Comparative example 2
Preparing a positive electrode material:
(1) lithium carbonate, ammonium ferromanganese phosphate (Mn/Fe ═ 6:4, (Mn + Fe)/P ═ 0.98:1), sucrose and water were mixed, and then ground in a sand mill at 2000rpm for 6 hours to obtain a slurry. Wherein the adding molar ratio of lithium carbonate (calculated by Li), manganese ferric ammonium phosphate and sucrose (calculated by C) is 1.02:1: 0.50. Drying and granulating the obtained slurry by a spray dryerSpray-dried material was obtained. The solid content of the slurry was 20 wt%, the particle size D of the slurry50Is 100 nm. The conditions of spray drying were: the air inlet temperature is 220 ℃, and the air outlet temperature is 100 ℃.
(2) And calcining the spray-dried material at 680 ℃ for 12h under the nitrogen protection atmosphere to obtain a sintered material.
(3) The sintering material is crushed by airflow and screened to obtain a matrix Li1.02(Mn0.6Fe0.4)0.98PO4The coating layer is the positive electrode material Li of C1.02(Mn0.6Fe0.4)0.98PO4and/C, recorded as D2. Average particle diameter D of D2503 μm, the average thickness of the coating layer was 8nm, the content of the coating layer was 2.36 wt%, and the porosity was 10%.
The cathode material D2 was assembled into button cell D2 according to the preparation method and was electrochemically characterized at 4.4-2.5V. The characterization results for button cell D2 are shown in table 1.
Example 1
Preparing a positive electrode material:
(1) lithium carbonate, iron phosphate (Fe/P ═ 0.97:1), sucrose, zirconium oxychloride, terephthalic acid and water were mixed and then ground in a sand mill at a rotation speed of 1800rpm for 3 hours to obtain a slurry. Wherein the adding molar ratio of lithium carbonate (calculated by Li), iron phosphate, cane sugar (calculated by C), zirconium oxychloride and terephthalic acid is 1.02:1:0.35:0.01: 0.01. And drying and granulating the obtained slurry by a spray dryer to obtain a spray-dried material. The solid content of the slurry was 40 wt%, the particle size D of the slurry50Is 400 nm. The conditions of spray drying were: the air inlet temperature is 230 ℃, and the air outlet temperature is 110 ℃.
(2) And calcining the spray-dried material at 720 ℃ for 12h under the nitrogen protection atmosphere to obtain a sintered material.
(3) The sintering material is crushed by airflow and screened to obtain a matrix Li1.02Fe0.97Zr0.01PO4The coating layer is a positive electrode material Li of graphitized porous carbon GPC (composition C)1.02Fe0.97Zr0.01PO4@ GPC, C1. Average particle diameter D of C1502 μm, a coating thickness of about 12nm, and coatingThe content of the layer was 1.24 wt%, the porosity was 30%.
Fig. 2 shows a scanning electron micrograph of the positive electrode material C1, and it can be seen from fig. 2 that the surface of the lithium iron phosphate positive electrode material C1 is coated with a graphitized porous carbon coating layer having a nano-scale thickness, and compared with fig. 1, the coating layer is distributed more uniformly, and there is no foreign matter obviously protruding from the particle surface. FIG. 5 is a Raman spectrum of the positive electrode materials obtained in example 1 and comparative example 1, in which the intensity ratio I of the D peak to the G peak of example 1D/IGMuch less than comparative example 1, indicating that example 1 has a higher degree of carbon-coated graphitization than comparative example 1.
The cathode material C1 was assembled into button cell C1 and electrochemically characterized according to the method of the preparation example. The characterization result of the button cell C1 is shown in Table 1, the button cell assembled by the positive electrode material C1 has a specific discharge capacity of 164.1mAh/g at 0.1C25 ℃ of 3.9-2.5V, a coulombic efficiency of 98.4% at 0.1C25 ℃, a specific first-cycle discharge capacity of 150.9mAh/g at 1C25 ℃, and a capacity retention rate of 99.9% after 80-cycle; compared with comparative example 1, the specific discharge capacity of 0.1C and 1C and the capacity retention rate after 80 weeks are both obviously improved.
The charge-discharge curve of the button cell C1 at 0.1C25 ℃ is shown in figure 3, and the discharge specific capacity curve of the button cell C1 at different multiplying factors is shown in figure 4. As can be seen from fig. 3 and 4, both the capacity and rate performance of the example 1 sample are superior to those of the comparative example 1.
Example 2
Preparing a positive electrode material:
(1) lithium carbonate, iron phosphate (Fe/P ═ 0.97:1), starch, nickel oxide, ammonium titanyl oxalate, 2-aminoterephthalic acid and water were mixed and then ground in a sand mill to obtain a slurry. Wherein the adding molar ratio of lithium carbonate (calculated by Li), iron phosphate, starch (calculated by C), nickel oxide, ammonium titanyl oxalate and trimesic acid is 1.04:1:0.45:0.005:0.015: 0.02. Drying and granulating the obtained slurry by a spray dryer to obtain spray-dried slurry, wherein the solid content of the slurry is 40 wt%, and the granularity D of the slurry50Is 400 nm. The conditions of spray drying were: the air inlet temperature is 205 ℃, and the air outlet temperature is 90 ℃.
(2) And calcining the spray-dried material for 10 hours at 720 ℃ under the nitrogen protection atmosphere to obtain a sintered material.
(3) Sieving the sintered material to obtain a matrix Li1.04Fe0.97Ni0.005Ti0.015PO4The coating layer is GPC-N (composition is CN)0.05) Positive electrode material Li1.04Fe0.97Ni0.005Ti0.015PO4@ GPC-N, denoted C2. Average particle diameter D of C2508 μm, the thickness of the coating layer was 8nm, the content of the coating layer was 1.28 wt%, and the porosity was 32%.
The cathode material C2 was assembled into button cells and electrochemically characterized according to the method of the preparation examples. The characterization results of the button cell are shown in table 1.
Example 3
Preparing a positive electrode material:
(1) mixing lithium hydroxide, iron phosphate (Fe/P is 0.97:1), fructose, molybdenum oxalate, magnesium acetate, 2-amino trimesic acid and 2, 5-dihydroxy-3-mercapto terephthalic acid with water, and grinding in a planetary ball mill at the rotation speed of 600rpm for 5h to obtain slurry. Wherein the addition molar ratio of lithium hydroxide, iron phosphate, fructose (calculated by C), molybdenum oxalate, magnesium acetate, 2-amino trimesic acid and 2, 5-dihydroxy-3-mercapto terephthalic acid is 1.03:1:0.40:0.01:0.01:0.015: 0.01. Drying and granulating the obtained slurry by a spray dryer to obtain spray-dried slurry, wherein the solid content of the slurry is 40 wt%, and the granularity D of the slurry50Is 350 nm. The conditions of spray drying were: the air inlet temperature is 210 ℃, and the air outlet temperature is 95 ℃.
(2) And calcining the spray-dried material at 740 ℃ for 9 hours under the nitrogen protection atmosphere to obtain a sintered material.
(3) The sintering material is crushed by airflow and screened to obtain a matrix Li1.03Fe0.97Mo0.01Mg0.01PO4The coating layer is GPC-NS (composition CN)0.1S0.05) Positive electrode material Li1.03Fe0.97Mo0.01Mg0.01PO4@ GPC-NS, denoted C3. Average particle diameter D of C3502 μm, a coating layer thickness of 15nm, and a coating layer content of1.21 wt%, porosity 35%.
The cathode material C3 was assembled into button cells and electrochemically characterized according to the method of the preparation examples. The characterization results of the button cell are shown in table 1.
Example 4
Preparing a positive electrode material:
(1) lithium hydroxide, iron phosphate (Fe/P ═ 0.97), glucose, aluminum citrate, hafnium oxide, trimesic acid and ethanol were mixed and then ground in a sand mill at a rotation speed of 1000rpm for 8 hours to obtain a slurry. Wherein the adding molar ratio of the lithium hydroxide, the iron phosphate, the glucose (calculated by C), the aluminum citrate, the hafnium oxide and the trimesic acid is 1.03:1:0.40:0.01:0.01: 0.015. Drying and granulating the obtained slurry by a spray dryer to obtain spray-dried slurry, wherein the solid content of the slurry is 35 wt%, and the granularity D of the slurry50Is 450 nm. The conditions of spray drying were: the air inlet temperature is 160 ℃, and the air outlet temperature is 70 ℃.
(2) And calcining the spray-dried material for 10 hours at 760 ℃ under the nitrogen protection atmosphere to obtain a sintered material.
(3) The sintering material is crushed by airflow and screened to obtain a matrix Li1.03Fe0.97Al0.01Hf0.01PO4The coating layer is positive electrode material Li of GPC (composition C)1.03Fe0.97Al0.01Hf0.01PO4@ GPC, C4. Average particle diameter D of C4502 μm, the thickness of the coating layer was 14nm, the content of the coating layer was 1.12 wt%, and the porosity was 33%.
The cathode material C4 was assembled into button cells and electrochemically characterized according to the method of the preparation examples. The characterization results of the button cell are shown in table 1.
Example 5
Preparing a positive electrode material:
(1) lithium carbonate, ammonium ferromanganese phosphate (Mn/Fe ═ 6:4, (Mn + Fe)/P ═ 0.98), glucose, and water were mixed, and then ground in a sand mill at 1000rpm for 12 hours to obtain a slurry. Wherein the adding molar ratio of lithium carbonate (calculated by Li), manganese ferric ammonium phosphate and glucose (calculated by C) is 1.01: 1: 0.50. Will be provided withAnd drying and granulating the obtained slurry by a spray dryer to obtain a spray-dried material. The solid content of the slurry was 20 wt%, the particle size D of the slurry50Is 120 nm. The conditions of spray drying were: the air inlet temperature is 220 ℃, and the air outlet temperature is 100 ℃.
(2) Physically mixing the spray-dried material with nano powder of a metal organic framework material UiO-66 according to the mass ratio of 100:1, and fully and uniformly mixing the mixture by using a mixer to obtain a coating material.
(3) And calcining the coating material at 680 ℃ for 12h under the nitrogen protection atmosphere to obtain a sintering material.
(4) The sintering material is crushed by airflow and screened to obtain a matrix Li1.01(Mn0.6Fe0.4)0.98Zr0.01PO4The coating layer is a positive electrode material of C, Li1.01(Mn0.6Fe0.4)0.98Zr0.01PO4and/GPC, as C5. Average particle diameter D of C5503 μm, the average thickness of the coating layer was 8nm, the content of the coating layer was 2.41 wt%, and the porosity was 25%.
The cathode material C5 was assembled into button cells for electrochemical characterization at 4.4-2.5V according to the preparation example. The characterization results of the button cell are shown in table 1.
Example 6
Preparing a positive electrode material:
(1) mixing lithium carbonate, manganese iron hydrogen phosphate (Mn/Fe is 6:4, (Mn + Fe)/P is 0.98:1), cane sugar, vanadium pentoxide and fumaric acid with water, and then grinding the mixture in a stirring mill and a sand mill to obtain slurry, wherein the rotation speed of the stirring mill is 600rpm, the time is 2 hours, the rotation speed of the sand mill is 2000rpm, and the time is 10 hours. Wherein the adding molar ratio of lithium carbonate (calculated by Li), manganese iron hydrogen phosphate, sucrose (calculated by C), vanadium pentoxide and fumaric acid is 1.04:1:0.42:0.01: 0.02. Drying and granulating the obtained slurry by a spray dryer to obtain spray-dried slurry, wherein the solid content of the slurry is 18 wt%, and the granularity D of the slurry50Is 80 nm. The conditions of spray drying were: the air inlet temperature is 205 ℃, and the air outlet temperature is 90 ℃.
(2) And calcining the spray-dried material at 650 ℃ for 12h under the nitrogen protection atmosphere to obtain a sintered material.
(3) Sieving the sintered material to obtain a matrix Li1.04(Mn0.6Fe0.4)0.98V0.01PO4The coating layer is positive electrode material Li of GPC (composition C)1.04(Mn0.6Fe0.4)0.98V0.01PO4@ GPC, C6. Average particle diameter D of C65010 μm, the thickness of the coating layer was 10nm, the content of the coating layer was 2.15 wt%, and the porosity was 55%.
The cathode material C6 was assembled into button cells for electrochemical characterization at 4.4-2.5V according to the preparation example. The characterization results of the button cell are shown in table 1.
Example 7
Preparing a positive electrode material:
(1) mixing lithium carbonate, manganese ferric ammonium phosphate (Mn/Fe is 7:3, (Mn + Fe)/P is 0.98:1), polyethylene glycol, magnesium acetate, 2-methylimidazole and pyromellitic acid with water, and then grinding the mixture in a stirring mill and a sand mill to obtain slurry, wherein the rotation speed of the stirring mill is 500rpm, the time is 3 hours, the rotation speed of the sand mill is 1800rpm, and the time is 8 hours. Wherein the adding molar ratio of lithium carbonate (calculated by Li), manganese ferric ammonium phosphate, polyethylene glycol (calculated by C), magnesium acetate, 2-methylimidazole and pyromellitic acid is 1.02:1:0.50:0.01:0.01: 0.05. Drying and granulating the obtained slurry by a spray dryer to obtain spray-dried slurry, wherein the solid content of the slurry is 20 wt%, and the granularity D of the slurry50Is 100 nm. The conditions of spray drying were: the air inlet temperature is 220 ℃ and the air outlet temperature is 105 ℃.
(2) And calcining the spray-dried material at 680 ℃ for 8h under the nitrogen protection atmosphere to obtain a sintered material.
(3) The sintering material is crushed by airflow and screened to obtain a matrix Li1.02(Mn0.7Fe0.3)0.98Mg0.01The coating layer is GPC-N (composition CN)0.1) Positive electrode material Li1.02(Mn0.7Fe0.3)0.98Mg0.01PO4@ GPC-N, denoted C7. Average particle diameter D of C7502.4 μm, the thickness of the coating layer was 12nm, the content of the coating layer was 2.32 wt%, and the porosity was 60%. .
The cathode material C7 was assembled into button cells for electrochemical characterization at 4.4-2.5V according to the preparation example. The characterization results of the button cell are shown in table 1.
TABLE 1
Note: GPC is used for graphitized porous carbon, the suffix-N is added to represent nitrogen doping, the suffix-NS is added to represent nitrogen-sulfur doping, and the like.
As can be seen from table 1, compared with comparative example 1, the specific discharge capacity of 0.1C, the coulombic efficiency, and the specific discharge capacity of 1C of examples 1, 2, 3, and 4 are all significantly improved. Compared with the comparative example 2, the specific discharge capacity of 0.1C, the coulombic efficiency, the specific discharge capacity of 1C and the retention rate of 1C80 cycle of the examples 5, 6 and 7 are all obviously improved. Therefore, the olivine-structure anode material comprising the coating layer provided by the invention has the advantages that the coating layer is of a graphitized porous carbon structure and can inherit the porosity of the metal organic framework material coating layer generated in situ in the material preparation process, compared with the traditional carbon coating, the graphitizing degree is higher, the lithium ion transmission channel is better, the electronic conductivity and the ionic conductivity of the olivine-structure anode material are favorably improved, and the electrochemical performance of the olivine-structure anode material prepared by the method is obviously improved.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (16)
1. The olivine-structure positive electrode material is characterized by comprising a substrate and a coating layer coated on the surface of the substrate;
the matrix has a composition represented by formula I:
Li1+a[(Fe1-xMnx)1-bMy]PO4formula I
Wherein M is at least one selected from La, Cr, Mo, Ca, Hf, Ti, Mn, Fe, Zn, Y, Zr, W, Nb, Sm, Co, Ni, V, Mg, Na, B and Al; a is more than or equal to 0.5 and less than or equal to 0.3, b is more than or equal to 0 and less than or equal to 0.4, x is more than or equal to 0 and less than or equal to 1, and y is more than 0 and less than or equal to 0.04;
the coating layer is graphitized porous carbon and has a composition represented by formula II:
CDvformula II
Wherein D is selected from at least one of N, P, Si, S, B, F and Cl; v is more than or equal to 0 and less than or equal to 0.4.
2. The positive electrode material according to claim 1, wherein M is at least one selected from Hf, Zr, Mg, Al, Ti, V, Mo, Ni, Co, Nb, and Na.
3. The positive electrode material according to claim 1 or 2, wherein D is at least one selected from N, P, Si, S, B, F and Cl.
4. The positive electrode material according to any one of claims 1 to 3, wherein the coating layer is contained in an amount of 0.01 to 5 wt%, preferably 0.5 to 2.5 wt%, based on the total weight of the positive electrode material.
5. The positive electrode material according to any one of claims 1 to 4, wherein the average particle diameter D of the positive electrode material50Is 0.05-5 μm, and the average thickness of the coating layer is 1-100 nm.
6. The positive electrode material according to any one of claims 1 to 5, wherein the porosity of the coating layer is 10 to 200%, preferably 20 to 100%.
7. A preparation method of an olivine-structure cathode material is characterized by comprising the following steps:
(1) mixing a lithium source, a precursor, a carbon source and a liquid medium, grinding the mixture to prepare slurry, and performing spray drying granulation to obtain a spray-dried material;
(2) calcining the spray-dried material in an inert atmosphere to obtain a sintered material;
(3) optionally crushing and screening the sintered material to obtain an olivine-structured positive electrode material;
wherein the method further comprises adding a metal source M, an organic ligand in step (1);
and/or, before the step (2), mixing the spray-dried material with the metal-organic framework material to obtain a mixed material.
8. The production method according to claim 7, wherein the lithium source is selected from at least one of lithium oxide, lithium hydroxide, lithium chloride, lithium nitrate, lithium nitrite, lithium formate, lithium acetate, lithium oxalate, lithium carbonate, lithium phosphate, dilithium hydrogen phosphate, and lithium dihydrogen phosphate;
preferably, the precursor is selected from at least one of iron phosphate, ferrous ammonium phosphate, ferrous manganese hydrogen phosphate and manganese hydrogen phosphate; or the precursor is selected from at least one of ferrous oxalate, ferrous manganese oxalate and a mixture selected from phosphoric acid and/or ammonium dihydrogen phosphate;
preferably, the carbon source is selected from at least one of glucose, sucrose, fructose, cellulose, starch, citric acid, polyacrylic acid, phenolic resin, polyethylene glycol, dopamine, graphene and carbon nanotubes;
preferably, the metal source M is selected from at least one of nitrates, hydrochlorides, sulfates, acetates, metal oxides, metal oxychlorides, metal hydroxides, carbonates, phosphates, metal clusters, metal complexes and metal carboxylates capable of providing the element M;
preferably, the organic ligand is selected from at least one of polycarboxyl organic acid, imidazole compounds, pyridine compounds and pyrimidine compounds;
preferably, the liquid medium is selected from at least one of water, methanol, ethanol, propanol, ethylene glycol, isopropanol, benzyl alcohol, acetone, benzene, toluene, methyl ether, diethyl ether, acetic acid, xylene, tetrahydrofuran, dimethyl carbonate, N-methylpyrrolidone, propylene carbonate, triethylamine, triethanolamine, N-dimethylformamide, N-diethylformamide, acetonitrile and ethylene glycol dimethyl ether.
9. The production method according to claim 7 or 8, wherein the lithium source, the precursor, the carbon source, the metal source M, and the organic ligand are added in a molar ratio of (1-1.1): (0.96-1.04): (0.25-1):(0-0.04):(0-0.04).
10. The production method according to any one of claims 7 to 9, wherein in step (1), the conditions for the milling include: ball-milling for 1-24h at the rotation speed of 100-600rpm by adopting a planetary ball mill;
and/or, adopting a stirring mill and/or a sand mill to perform ball milling for 0.5-10h at the rotating speed of 300-3000 rpm.
11. The production method according to any one of claims 7 to 10, wherein in step (1), the solid content of the slurry is 10 to 70 wt%, and the particle size D of the slurry is50Is 50-5000 nm.
12. The production method according to any one of claims 7 to 11, wherein in the step (1), the conditions of the spray drying include: the air inlet temperature is 180 ℃ and 280 ℃, and the air outlet temperature is 70-140 ℃.
13. The production method according to any one of claims 7 to 12, wherein the conditions of the calcination include: the calcination temperature is 500-900 ℃, preferably 600-800 ℃; the calcination time is 4-20h, preferably 6-15 h.
14. An olivine-structured positive electrode material obtained by the production method according to any one of claims 7 to 13;
preferably, the positive electrode material comprises a substrate and a coating layer coated on the surface of the substrate;
the matrix has a composition represented by formula I:
Li1+a[(Fe1-xMnx)1-bMy]PO4formula I
Wherein M is at least one selected from La, Cr, Mo, Ca, Hf, Ti, Mn, Fe, Zn, Y, Zr, W, Nb, Sm, Co, Ni, V, Mg, Na, B and Al; a is more than or equal to 0.5 and less than or equal to 0.3, b is more than or equal to 0 and less than or equal to 0.4, x is more than or equal to 0 and less than or equal to 1, and y is more than 0 and less than or equal to 0.04;
the coating layer is graphitized porous carbon and has a composition represented by formula II:
CDvformula II
Wherein D is independently selected from at least one of N, P, Si, S, B, F and Cl; v is more than or equal to 0 and less than or equal to 0.4.
15. Use of the olivine structure positive electrode material of any of claims 1 to 6 and 14 in a lithium ion battery.
16. A lithium ion battery, wherein the positive electrode material of the lithium ion battery is the olivine-structure positive electrode material according to any one of claims 1 to 6 and 14.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113929069A (en) * | 2021-10-08 | 2022-01-14 | 中国科学院过程工程研究所 | Manganese-rich phosphate cathode material, preparation method and application thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1958440A (en) * | 2006-11-24 | 2007-05-09 | 中南大学 | Method for synthesizing Nano level powder of lithium iron phosphate |
| CN103187569A (en) * | 2013-03-31 | 2013-07-03 | 复旦大学 | Preparation method for LiFePO4/C contained anode material for lithium ion battery |
| CN108199041A (en) * | 2017-12-29 | 2018-06-22 | 桑德集团有限公司 | A kind of modified phosphate iron lithium material, preparation method and application |
| CN109616653A (en) * | 2018-12-12 | 2019-04-12 | 上海航天电源技术有限责任公司 | Phosphate composite positive pole and preparation method derived from a kind of metal organic frame |
| CN111224103A (en) * | 2020-01-17 | 2020-06-02 | 贝特瑞（天津）纳米材料制造有限公司 | Preparation method of metal ion-doped high-rate mesoporous lithium iron phosphate cathode material |
-
2021
- 2021-04-27 CN CN202110461007.3A patent/CN113363483A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1958440A (en) * | 2006-11-24 | 2007-05-09 | 中南大学 | Method for synthesizing Nano level powder of lithium iron phosphate |
| CN103187569A (en) * | 2013-03-31 | 2013-07-03 | 复旦大学 | Preparation method for LiFePO4/C contained anode material for lithium ion battery |
| CN108199041A (en) * | 2017-12-29 | 2018-06-22 | 桑德集团有限公司 | A kind of modified phosphate iron lithium material, preparation method and application |
| CN109616653A (en) * | 2018-12-12 | 2019-04-12 | 上海航天电源技术有限责任公司 | Phosphate composite positive pole and preparation method derived from a kind of metal organic frame |
| CN111224103A (en) * | 2020-01-17 | 2020-06-02 | 贝特瑞（天津）纳米材料制造有限公司 | Preparation method of metal ion-doped high-rate mesoporous lithium iron phosphate cathode material |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN113929069B (en) * | 2021-10-08 | 2023-09-22 | 中国科学院过程工程研究所 | A kind of manganese-rich phosphate cathode material and its preparation method and application |
| CN114220967A (en) * | 2021-11-09 | 2022-03-22 | 厦门厦钨新能源材料股份有限公司 | Olivine type phosphate active material, preparation method and application thereof |
| CN114373912B (en) * | 2021-12-31 | 2023-09-08 | 江苏贝特瑞纳米科技有限公司 | Fluorine-doped lithium iron manganese phosphate positive electrode material and preparation method thereof |
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| CN114373912A (en) * | 2021-12-31 | 2022-04-19 | 江苏贝特瑞纳米科技有限公司 | Fluorine-doped lithium manganese iron phosphate cathode material and preparation method thereof |
| CN114335475B (en) * | 2021-12-31 | 2024-01-16 | 珠海冠宇电池股份有限公司 | Metal fluoride/porous carbon composite positive electrode material, positive electrode plate comprising same and battery |
| CN114530595A (en) * | 2022-01-21 | 2022-05-24 | 珠海冠宇电池股份有限公司 | Lithium iron manganese phosphate positive electrode material, positive plate comprising same and battery |
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