WO2021175233A1 - 一种富锂锰基材料及其制备方法和应用 - Google Patents

一种富锂锰基材料及其制备方法和应用 Download PDF

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WO2021175233A1
WO2021175233A1 PCT/CN2021/078797 CN2021078797W WO2021175233A1 WO 2021175233 A1 WO2021175233 A1 WO 2021175233A1 CN 2021078797 W CN2021078797 W CN 2021078797W WO 2021175233 A1 WO2021175233 A1 WO 2021175233A1
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lithium
rich manganese
amount
salt
based material
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PCT/CN2021/078797
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English (en)
French (fr)
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王俊
刘亚飞
陈彦彬
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北京当升材料科技股份有限公司
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Priority to EP21763737.0A priority Critical patent/EP4047688A4/en
Priority to JP2022522824A priority patent/JP7204049B2/ja
Priority to US17/778,468 priority patent/US11958757B2/en
Priority to KR1020227012359A priority patent/KR102477330B1/ko
Publication of WO2021175233A1 publication Critical patent/WO2021175233A1/zh

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    • H—ELECTRICITY
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    • C01G45/00—Compounds of manganese
    • C01G45/12—Manganates manganites or permanganates
    • C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
    • C01G45/1228—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [MnO2]n-, e.g. LiMnO2, Li[MxMn1-x]O2
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    • C01G51/44—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese
    • C01G51/50—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese of the type [MnO2]n-, e.g. Li(CoxMn1-x)O2, Li(MyCoxMn1-x-y)O2
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    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Definitions

  • the present invention relates to the technical field of lithium-ion batteries, in particular to a lithium-rich manganese-based material, a method for preparing a lithium-rich manganese-based material, and a lithium-rich manganese-based material prepared by the method.
  • the lithium-rich manganese-based material is Application in lithium-ion batteries.
  • the positive electrode As the core key material of the lithium-ion battery, directly determines the technical performance level of the battery.
  • commercial cathode materials mainly include layered LiMO 2 (M is Ni, Co, Mn, etc.), spinel-type LiMn 2 O 4 and olivine-type LiFePO 4 .
  • LiCoO 2 has a high cost
  • LiMn 2 O 4 with a spinel structure is prone to crystal form transformation during recycling.
  • the layered lithium-rich manganese-based material has attracted wide attention due to its high specific capacity (>250mAh/g), high safety and low price, and has become a new generation of power-type lithium-ion battery cathode material with the most development potential. .
  • the material will transform from a layered structure to a spinel structure during the cycle, resulting in severe voltage attenuation, lowering the energy density of the material, and increasing the difficulty of the battery management system, which seriously hinders its commercial application process.
  • the purpose of the present invention is to overcome the defects that lithium-rich manganese-based materials in the prior art are prone to structural transformation and poor cycle performance during the cycle.
  • the first aspect of the present invention provides a lithium-rich manganese-based material
  • the lithium-rich manganese-based material includes a substrate and a coating layer covering the surface of the substrate;
  • the matrix contains a substance with a chemical formula Li 1.2+x [(Mn a Co b Ni c M 1-abc ) 1-d M′ d ] 0.8-x O 2
  • the coating layer contains a chemical formula Na u [Li v (Mn a Co b Ni c M 1-abc ) ⁇ M′ 1-v- ⁇ ]O 2 substance, where -0.2 ⁇ x ⁇ 0.3, 0.5 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.5, 0 ⁇ d ⁇ 0.1, 0.4 ⁇ u ⁇ 5/6, 0 ⁇ v ⁇ 0.5, 0.5 ⁇ 1, M and M'are each independently selected from Al, B, Ba, Ce, Cr , Cu, Fe, K, La, Mg, Mo, Na, Nb, Os, Pr, Re, Ru, Sc, Sr, Sm, Ta, Ti, V, W, Y, Yb, Zn, Zrkind of element
  • the thickness of the coating layer is 10-100 nm.
  • the second aspect of the present invention provides a method for preparing a lithium-rich manganese-based material, the method comprising:
  • the lithium-rich manganese-based precursor material is sintered with each component in component A to obtain a lithium-rich manganese-based material.
  • the component A contains lithium salt and sodium salt, and the component A optionally contains It contains a first dopant, and the first dopant contains the element M′;
  • the lithium-rich manganese-based precursor material is selected from at least one substance in the chemical formula Mn a Co b Ni c M 1-abc (OH) 2 and Mn a Co b Ni c M 1-abc CO 3;
  • M and M' are each independently selected from Al, B, Ba, Ce, Cr, Cu, Fe, K, La, Mg, Mo At least one element of, Na, Nb, Os, Pr, Re, Ru, Sc, Sr, Sm, Ta, Ti, V, W, Y, Yb, Zn, Zr;
  • the molar ratio of the amount of the first dopant to the sum of the amount of the lithium-rich manganese-based precursor material and the amount of the first dopant is 0-0.1:1; the amount of the lithium salt is relative to the amount of the first dopant.
  • the molar ratio of the sum of the amounts of the lithium-rich manganese-based precursor material and the first dopant is 1.0-1.6:1, and the molar ratio of the amount of the sodium salt to the amount of the lithium salt is 0.005-0.3: 1.
  • the amount of the first dopant is based on the M'element contained therein, and the amount of the lithium-rich manganese-based precursor material is based on the sum of the Mn, Co, Ni, M elements contained therein, and the lithium
  • the amount of the salt is based on the Li element contained therein, and the amount of the sodium salt is based on the Na element contained therein.
  • the third aspect of the present invention provides a lithium-rich manganese-based material prepared by the method described in the foregoing second aspect.
  • the fourth aspect of the present invention provides the application of the lithium-rich manganese-based material described in the first aspect or the third aspect in a lithium ion battery.
  • the technical solution provided by the present invention has at least the following advantages:
  • the lithium-rich manganese-based material provided by the present invention has excellent cycling performance, low voltage attenuation during electrochemical cycling, and stable structure.
  • the lithium-rich manganese-based material provided by the present invention has higher discharge specific capacity, high first-time efficiency and excellent rate performance.
  • the lithium-rich manganese-based material provided by the present invention has the advantages of small specific surface area and large tap density, which is beneficial to reduce side reactions with the electrolyte and increase the volume energy density of the battery.
  • the preparation method provided by the present invention has simple process, no pollution, simple introduction of doping elements and coating layer, controllable process, and is suitable for industrialized production.
  • Figure 1 is a graph of XRD test results of materials prepared in Example 1 and Comparative Example 1-2;
  • Example 2 is a scanning electron microscope image of the lithium-rich manganese-based material prepared in Example 1;
  • Figure 3 is a scanning electron microscope image of the matrix material prepared in Comparative Example 1;
  • Example 5 is a graph showing the first charge and discharge curve of the lithium-rich manganese-based material prepared in Example 1;
  • Example 6 is a graph showing the test results of rate performance of the lithium-rich manganese-based material prepared in Example 1;
  • FIG. 7 is a graph of the cycle performance test results of the materials obtained in Example 1 and Comparative Example 1.
  • FIG. 7 is a graph of the cycle performance test results of the materials obtained in Example 1 and Comparative Example 1.
  • the room temperature means 25 ⁇ 2°C.
  • the first aspect of the present invention provides a lithium-rich manganese-based material
  • the lithium-rich manganese-based material includes a substrate and a coating layer covering the surface of the substrate;
  • the matrix contains a substance with a chemical formula Li 1.2+x [(Mn a Co b Ni c M 1-abc ) 1-d M′ d ] 0.8-x O 2
  • the coating layer contains a chemical formula Na u [Li v (Mn a Co b Ni c M 1-abc ) ⁇ M′ 1-v- ⁇ ]O 2 substance, where -0.2 ⁇ x ⁇ 0.3, 0.5 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.5, 0 ⁇ d ⁇ 0.1, 0.4 ⁇ u ⁇ 5/6, 0 ⁇ v ⁇ 0.5, 0.5 ⁇ 1, M and M'are each independently selected from Al, B, Ba, Ce, Cr , Cu, Fe, K, La, Mg, Mo, Na, Nb, Os, Pr, Re, Ru, Sc, Sr, Sm, Ta, Ti, V, W, Y, Yb, Zn, Zrkind of element
  • the thickness of the coating layer is 10-100 nm.
  • the matrix contains a substance with an O3-type structure of the chemical formula Li 1.2+x [(Mn a Co b Ni c M 1-abc ) 1-d M′ d ] 0.8-x O 2.
  • the coating layer contains a P2-type structural substance of the chemical formula Na u [Li v (Mn a Co b Ni c M 1-abc ) ⁇ M′ 1-v- ⁇ ]O 2.
  • the coating includes the coating layer attached to the surface of the substrate.
  • the median diameter D50 of the lithium-rich manganese-based material is 5-15 ⁇ m.
  • the specific surface area of the lithium-rich manganese-based material is 0.2-8 m 2 /g, and the tap density of the lithium-rich manganese-based material is 1.4-2.0 g/cm 3 .
  • the second aspect of the present invention provides a method for preparing a lithium-rich manganese-based material, the method comprising:
  • the lithium-rich manganese-based precursor material is sintered with each component in component A to obtain a lithium-rich manganese-based material.
  • the component A contains lithium salt and sodium salt, and the component A optionally contains It contains a first dopant, and the first dopant contains the element M′;
  • the lithium-rich manganese-based precursor material is selected from at least one substance in the chemical formula Mn a Co b Ni c M 1-abc (OH) 2 and Mn a Co b Ni c M 1-abc CO 3;
  • M and M' are each independently selected from Al, B, Ba, Ce, Cr, Cu, Fe, K, La, Mg, Mo At least one element of, Na, Nb, Os, Pr, Re, Ru, Sc, Sr, Sm, Ta, Ti, V, W, Y, Yb, Zn, Zr;
  • the molar ratio of the amount of the first dopant to the sum of the amount of the lithium-rich manganese-based precursor material and the amount of the first dopant is 0-0.1:1; the amount of the lithium salt is relative to the amount of the first dopant.
  • the molar ratio of the sum of the amounts of the lithium-rich manganese-based precursor material and the first dopant is 1.0-1.6:1, and the molar ratio of the amount of the sodium salt to the amount of the lithium salt is 0.005-0.3: 1.
  • the amount of the first dopant is based on the M'element contained therein, and the amount of the lithium-rich manganese-based precursor material is based on the sum of the Mn, Co, Ni, M elements contained therein, and the lithium
  • the amount of the salt is based on the Li element contained therein, and the amount of the sodium salt is based on the Na element contained therein.
  • the molar ratio of the amount of the first dopant to the sum of the amount of the lithium-rich manganese-based precursor material and the first dopant is 0-0.1 :1, refers to the amount of the first dopant based on the M'element contained therein and the lithium-rich manganese-based precursor material based on the sum of the Mn, Co, Ni, and M elements contained therein, and
  • the molar ratio of the amount of the sodium salt to the amount of the lithium salt is 0.005-0.3:1, which means that the sodium salt is calculated based on the sodium element contained therein.
  • the amount of the lithium salt, the sodium salt, the first dopant and the lithium-rich manganese-based precursor material is such that the obtained lithium-rich manganese-based material has Features of the lithium-rich manganese-based material described in the foregoing first aspect.
  • the sintering conditions include: performing the first sintering in an oxygen-containing atmosphere or a nitrogen atmosphere, heating from room temperature to 300-600°C, holding for 0-6 hours, and then performing the first sintering. Continue to heat up to 650-1000°C and keep it for 4-20h for the second sintering.
  • the temperature is directly raised from room temperature to 650-1000° C., and the second sintering is performed.
  • the lithium salt is selected from at least one of lithium carbonate, lithium hydroxide, lithium chloride, lithium nitrate, and lithium sulfate.
  • the sodium salt is selected from at least one of sodium carbonate, sodium bicarbonate, sodium oxalate, sodium acetate, sodium citrate, sodium chloride, sodium nitrate, sodium sulfate, and sodium hydroxide.
  • the first dopant is selected from at least one of oxides containing element M', phosphates containing element M', fluorides containing element M', and carbonates containing element M'.
  • the method further includes preparing the lithium-rich manganese-based precursor material through the following steps:
  • each component in component B is subjected to a co-precipitation reaction to obtain the lithium-rich manganese-based precursor material, wherein the component B contains a manganese salt, a precipitating agent and a complexing agent, and optionally, the B further contains at least one of a nickel salt, a cobalt salt, and a second dopant, and the second dopant contains the element M.
  • the amount of the manganese salt, the precipitation agent, the complexing agent, the nickel salt, the cobalt salt, and the second dopant is such that the obtained lithium-rich manganese-based precursor material is selected from
  • the chemical formula is at least one of Mn a Co b Ni c M 1-abc (OH) 2 and Mn a Co b Ni c M 1-abc CO 3 , where 0.5 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.5.
  • the precipitating agent is selected from at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate.
  • the lithium-rich manganese-based precursor material is selected from at least one substance in the chemical formula Mn a Co b Ni c M 1-abc (OH) 2
  • the lithium-rich manganese-based precursor material is selected from at least one substance in the chemical formula Mn a Co b Ni c M 1-abc CO 3.
  • the complexing agent is selected from at least one of ammonia, salicylic acid, ammonium sulfate, and ammonium chloride.
  • the concentration of the complexing agent is 2-10 mol/L.
  • the concentration of the precipitation agent is 4-10 mol/L.
  • the amount of the complexing agent and the precipitating agent is such that the pH value of the reaction system is 7-12.
  • the second dopant is selected from at least one of an oxide containing element M, a phosphate containing element M, a fluoride containing element M, and a carbonate containing element M.
  • the manganese salt, the cobalt salt, and the nickel salt are each independently selected from at least one of its sulfate, nitrate, chloride, acetate, and citrate, for example, the manganese salt At least one selected from the group consisting of manganese sulfate, manganese nitrate, manganese chloride, manganese acetate, and manganese citrate; the cobalt salt is selected from at least one of cobalt sulfate, cobalt nitrate, cobalt chloride, cobalt acetate, and cobalt citrate Species; the nickel salt is selected from at least one of nickel sulfate, nickel nitrate, nickel chloride, nickel acetate, and nickel citrate.
  • the conditions of the co-precipitation reaction include: carrying out in a reactor, a temperature of 20-60° C., a pH of 7-12, a stirring speed of 300-1000 rpm, and a reaction time of 10-30 h.
  • the co-precipitation reaction is carried out in the reactor, and the conditions of the co-precipitation reaction include: a temperature of 20-60° C., a pH value of 7-12, a stirring speed of 300-1000 rpm, and a reaction time of 10-30 hours to obtain lithium-rich manganese Base precursor material.
  • the method according to the second aspect of the present invention includes:
  • each component in component B is subjected to a co-precipitation reaction to obtain the lithium-rich manganese-based precursor material, wherein the component B contains manganese salt, precipitating agent and complexing And the B optionally further contains at least one of a nickel salt, a cobalt salt, and a second dopant, the second dopant contains the element M, and the conditions of the co-precipitation reaction include: temperature The temperature is 20-60°C, the pH is 7-10, the stirring speed is 300-1000rpm, and the reaction time is 10-30h;
  • step (2) Sintering the lithium-rich manganese-based precursor material obtained in step (1) with each component in component A to obtain a lithium-rich manganese-based material, said component A containing lithium salt and sodium salt, and
  • the component A optionally further contains a first dopant, the first dopant contains element M, and the sintering conditions include: in an oxygen-containing atmosphere or a nitrogen atmosphere, the temperature is raised from room temperature to 300 -600°C, holding for 0-6h for the first sintering, then continue to heat up to 650-1000°C, holding for 4-20h for the second sintering.
  • the method described in the second aspect of the present invention also includes post-processing methods known in the art such as suction filtration, washing, drying, crushing, and screening. limit.
  • the third aspect of the present invention provides a lithium-rich manganese-based material prepared by the method described in the second aspect.
  • the lithium-rich manganese-based material includes a substrate and a coating layer covering the surface of the substrate, and the substrate contains a chemical formula of Li 1.2+x [(Mn a Co b Ni c M 1-abc ) 1 -d M′ d ] 0.8-x O 2 substance, the coating layer contains the chemical formula Na u [Li v (Mn a Co b Ni c M 1-abc ) ⁇ M′ 1-v- ⁇ ]O 2 substances, where -0.2 ⁇ x ⁇ 0.3, 0.5 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.5, 0 ⁇ d ⁇ 0.1, 0.4 ⁇ u ⁇ 5/6, 0 ⁇ v ⁇ 0.5 , 0.5 ⁇ 1, M and M'are each independently selected from Al, B, Ba, Ce, Cr, Cu, Fe, K, La, Mg, Mo, Na, Nb, Os, Pr, Re, Ru, At least one element of Sc, Sr, Sm, Ta, Ti, V, W, Y,
  • the thickness of the coating layer is 10-100 nm.
  • the median diameter D50 of the lithium-rich manganese-based material is 5-15 ⁇ m.
  • the specific surface area of the lithium-rich manganese-based material is 0.2-8 m 2 /g, and the tap density of the lithium-rich manganese-based material is 1.4-2.0 m 3 /g.
  • the capacity of the coating layer is extremely low (approximately zero), but the inventors unexpectedly found that by generating the coating layer in situ on the surface of the substrate, the obtained lithium-rich manganese-based material is not only It has excellent rate performance and cycle performance, as well as excellent discharge capacity.
  • the fourth aspect of the present invention provides the application of the lithium-rich manganese-based material described in the first aspect or the third aspect in a lithium ion battery.
  • Phase test Tested by a 9kw X-ray diffractometer of SmartLab from Rigaku Corporation;
  • pole pieces Preparation of pole pieces: mix lithium-rich manganese-based materials, carbon black, polyvinylidene fluoride with an appropriate amount of N-methylpyrrolidone at a mass ratio of 80:10:10 to form a uniform slurry, and coat it on the aluminum foil. Drying, rolling, and punching at 120°C to prepare a positive electrode sheet with a diameter of 11 mm, the loading amount of the lithium-rich manganese-based material is about 7 mg/cm 2 .
  • a lithium sheet is used as the negative electrode
  • a polypropylene microporous membrane is used as the diaphragm (Celgard 2400)
  • 1M LiPF 6 /EC+DMC is used as the electrolyte to assemble a 2025 button battery.
  • the Xinwei battery test system is used to test the electrochemical performance of the 2025 button battery, where the 1C charge and discharge current density is 250mA/g:
  • step (2) Mix the lithium carbonate, sodium carbonate and the lithium-rich manganese-based material precursor material prepared in step (1) uniformly, and then heat up in an air atmosphere from room temperature to 450°C, keep it for 4 hours for the first sintering, and then heat up The temperature is kept at 850°C for 10 hours for second sintering, natural cooling, and then crushed and sieved to obtain lithium-rich manganese-based material S1.
  • the amount of the lithium carbonate based on the Li element contained therein and the amount of the lithium-rich manganese based material precursor material based on the sum of the Ni, Co, and Mn elements contained therein are moles
  • Example 2 In a similar manner to Example 1, the difference is that the formula or process parameters used are different, and the rest are the same as in Example 1, and the lithium-rich manganese-based materials S2-S7 are prepared. See Table 1 for details.
  • the ratio and the amount ratio are both molar ratios.
  • the difference is: no sodium salt is added in step (2), and the amount of lithium carbonate based on the Li element contained therein is compared with the Ni, Co, and Mn elements contained therein.
  • step (2) the addition amount of lithium salt and sodium salt is different, specifically:
  • the coating material D2 is prepared.
  • a lithium-rich manganese-based material D3 with a coating thickness of about 185 nm was prepared.
  • step (2) of Example 1 Using a method similar to that of Example 1, except that: in step (2) of Example 1, no sodium salt was added, and the amount of lithium carbonate based on the Li element contained therein was compared with the amount of lithium carbonate contained therein.
  • step (2) of Example 1 the amount of lithium salt and sodium salt added is different, specifically: the carbonic acid based on the Li element contained therein
  • S3 Ball mill the coating material D2 prepared by S2 for 5 hours, then mix it with the base material D1 prepared by S1 at a weight ratio of 1:10, and then heat it up from room temperature to 450°C in an air atmosphere and keep it warm for 4 hours.
  • the temperature is increased to 850° C., and the temperature is kept for 10 hours for the second sintering.
  • crushing and screening are carried out to obtain the lithium-rich manganese-based material D4 prepared by direct mixing and sintering.
  • a lithium-rich manganese-based material D4 with a coating thickness of about 370 nm was prepared.
  • a lithium-rich manganese-based material D5 with a coating thickness of about 50 nm was prepared.
  • composition of the material prepared in the above example is shown in Table 2.
  • the present invention tested the XRD of the lithium-rich manganese-based materials prepared in the above examples, and exemplarily provided the XRD test results of Example 1 and Comparative Examples 1-2, as shown in Figure 1, which can be seen from Figure 1.
  • the lithium-rich manganese-based material provided by the present invention is a two-phase composite structure of O3 type matrix material and P2 type coating layer material.
  • the present invention tested the scanning electron microscope images of the lithium-rich manganese-based materials prepared in the above examples, and exemplarily provided SEM images of Example 1 and Comparative Examples 1-2. The results are shown in Figure 2, Figure 3 and Figure 4, respectively. As shown, it can be seen from FIG. 2 that the lithium-rich manganese-based material provided by the present invention successfully coats the matrix material with the coating layer material; it can be seen from FIG. 3 that the matrix material is a secondary spherical structure formed by primary particles ; It can be seen from Figure 4 that the coating material is also a secondary spherical structure formed by primary particles.
  • the present invention tested the median diameter D 50 , tap density and specific surface area of the lithium-rich manganese-based materials prepared in the above examples, and the specific results are shown in Table 3.
  • Example 1 11.9 1.80 6.3
  • Example 2 10.5 1.88 0.3
  • Example 3 16.3 1.85 4.8
  • Example 4 6.8 1.75 0.6
  • Example 5 9.6 1.82 4.1
  • Example 6 14.0 1.87 2.4
  • Example 7 6.2 2.0 1.1 Comparative example 1 10.1 1.70 7.7 Comparative example 2 11.2 1.68 6.5 Comparative example 3 12.0 1.75 6.5 Comparative example 4 12.2 1.65 5.1 Comparative example 5 12.0 1.78 5.8
  • the lithium-rich manganese-based material provided by the present invention has a higher tap density and a lower specific surface area than the base material and the coating layer material.
  • the present invention tested the electrochemical properties of the materials prepared by the above examples, including the first charge-discharge specific capacity, the first efficiency, the cycle performance, the rate performance and the pressure drop.
  • the specific test results are shown in Table 4.
  • Example 1 From the comparison of the results of Example 1 and Comparative Example 1, it can be seen that the lithium-rich manganese-based material provided by the present invention, compared with the matrix material prepared in Comparative Example 1, the discharge specific capacity at 0.1C increased by 42 mAh/g, the first time efficiency Increased by 8%, the 1C discharge specific capacity increased by 39mAh/g, the 100-week capacity retention rate increased by 24%, and the average voltage attenuation decreased by 140mV. It can be seen that the lithium-rich manganese-based material provided by the present invention significantly improves the matrix material Performance.
  • the lithium-rich manganese-based material provided by the present invention has a discharge specific capacity of 75 mAh/g at 0.1C, which is the first time the efficiency is improved. 15%, the 1C discharge specific capacity increased by 72mAh/g, the 100-week capacity retention rate increased by 3.7%, and the average voltage attenuation decreased by 20mV. It can be seen that it is particularly required to control the thickness of the coating layer to 10-100nm When the lithium-rich manganese-based material has excellent discharge specific capacity, rate performance and cycle performance.
  • the lithium-rich manganese-based material provided by the present invention has a discharge specific capacity of 50 mAh/g at 0.1C, which is the first time the efficiency is improved. 12%, the 1C discharge specific capacity increased by 47mAh/g, the 100-week capacity retention rate increased by 18.8%, and the average voltage attenuation decreased by 50mV. It can be seen that the method for preparing lithium-rich manganese-based materials provided by the present invention is prepared by Lithium-rich manganese-based materials have better cycle performance and higher specific discharge capacity.
  • the lithium-rich manganese-based material provided by the present invention compared with the material prepared in Comparative Example 5, has a discharge specific capacity of 44mAh/g at 0.1C, which is the first time the efficiency is improved. 10%, the 1C discharge specific capacity increased by 46mAh/g, the 100-week capacity retention rate increased by 9.8%, and the average voltage attenuation decreased by 28mV. It can be seen that the method for preparing lithium-rich manganese-based materials provided by the present invention is prepared by Lithium-rich manganese-based materials have better cycle performance and higher specific discharge capacity.
  • the present invention exemplarily provides the first charge-discharge curve test result graph of the lithium-rich manganese-based material prepared in Example 1, as shown in FIG. 5.
  • the lithium-rich manganese-based material provided by the present invention is 0.1
  • the specific discharge capacity of C can reach 295mAh/g, and the first efficiency can reach 94%.
  • the present invention exemplarily provides a graph of the rate performance test results of the lithium-rich manganese-based material prepared in Example 1. As shown in FIG. 6, it can be seen from FIG. 6 that the lithium-rich manganese-based material provided by the present invention has excellent Magnification performance.
  • the present invention exemplarily provides the cycle performance of the materials prepared in Example 1 and Comparative Example 1. As shown in FIG. 7, it can be seen from FIG. 7 that the lithium-rich manganese-based material provided by the present invention has excellent cycle performance.
  • the lithium-rich manganese-based material provided by the present invention has excellent charge-discharge specific capacity, high first-effect performance, excellent rate performance and cycle performance.
  • the specific discharge capacity of the coating material of the present invention is extremely low (approximately zero), but the lithium-rich manganese-based material provided by the present invention not only has excellent rate performance and cycle performance, but also has excellent specific discharge capacity Compared with its individual base material and cladding material, its comprehensive performance has been significantly improved.

Abstract

本发明涉及锂离子电池技术领域，公开了一种富锂锰基材料及其制备方法和应用，该材料含有基体以及包覆在所述基体表面的包覆层，所述基体中含有化学式为Li1.2+x[(MnaCobNicM1-a-b-c)1-dM'd]0.8-xO2的物质，所述包覆层中含有化学式为Nau[Liv(MnaCobNicM1-a-b-c)γM'1-v-γ]O2的物质，在所述富锂锰基材料中，所述包覆层的厚度为10-100nm。本发明提供的富锂锰基材料具有高的首次效率、优异的循环性能、高的放电比容量和良好的倍率性能等。

Description

一种富锂锰基材料及其制备方法和应用
相关申请的交叉引用
本申请要求2020年03月30日提交的中国专利申请202010238007.2的权益，该申请的内容通过引用被合并于本文；
本申请要求2020年03月3日提交的中国专利申请202010140946.3的权益，该申请的内容通过引用被合并于本文。
技术领域
本发明涉及锂离子电池技术领域，具体涉及一种富锂锰基材料、一种制备富锂锰基材料的方法及由该方法制备得到的富锂锰基材料、所述富锂锰基材料在锂离子电池中的应用。
背景技术
在锂离子电池中，正极作为锂离子电池的核心关键材料，直接决定着电池的技术性能水平。随着各应用领域对锂离子电池能量密度要求的不断提高，商业化的正极材料主要包括层状LiMO 2(M为Ni、Co、Mn等)，尖晶石型LiMn 2O 4和橄榄石型LiFePO 4。其中，LiCoO 2成本高，尖晶石结构的LiMn 2O 4在循环使用过程中容易发生晶型转变Jahn-Teller(姜-泰勒)效应和锰离子的溶解，导致电池容量衰减快，高温性能差；层状正极材料LiNi 1-x-yCo xMn yO 2由于Ni、Co、Mn的协同效应，使材料成本降低、性能提升，但实际比容量并没有很大的突破，已难以满足人们的需求。
而层状富锂锰基材料凭借其高比容量(>250mAh/g)、高安全性和价格便宜等优点，受到人们的广泛关注，成为最具发展潜力的新一代动力型锂离子电池正极材料。但是，该材料在循环过程中会由层状结构向尖晶石结构转变，导致严重的电压衰减，使材料的能量密度降低，同时加大了电池管理系统的难度，严重阻碍了其商业化应用进程。
因此，开发一种具有高比容量、高安全性同时具有优异循环性能的富锂锰基正极材料具有非常重要的意义。
发明内容
本发明的目的是为了克服现有技术中富锂锰基材料存在的循环过程中易发生结构转变，循环性能较差的缺陷。
为了实现上述目的，本发明的第一方面提供一种富锂锰基材料，该富锂锰基材料含有基体以及包覆在所述基体表面的包覆层；
所述基体中含有化学式为Li 1.2+x[(Mn aCo bNi cM 1-a-b-c) 1-dM′ d] 0.8-xO 2的物质，所述包覆层中含有化学式为Na u[Li v(Mn aCo bNi cM 1-a-b-c) γM′ 1-v-γ]O 2的物质，其中，-0.2≤x≤0.3，0.5≤a≤1，0≤b≤0.5，0≤c≤0.5，0≤d≤0.1，0.4≤u<5/6，0≤v≤0.5，0.5≤γ≤1，M和M'各自独立地选自Al、B、Ba、Ce、Cr、Cu、Fe、K、La、Mg、Mo、Na、Nb、Os、Pr、Re、Ru、Sc、Sr、Sm、Ta、Ti、V、W、Y、Yb、Zn、Zr中的至少一种元素；
在所述材料中，所述包覆层的厚度为10-100nm。
本发明的第二方面提供一种制备富锂锰基材料的方法，该方法包括：
将富锂锰基前驱体材料与组分A中的各组分进行烧结，得到富锂锰基材料，所述组分A中含有锂盐、钠盐，并且所述组分A中任选还含有第一掺杂剂，所述第一掺杂剂中含有元素M′；
其中，所述富锂锰基前驱体材料选自化学式为Mn aCo bNi cM 1-a-b-c(OH) 2和Mn aCo bNi cM 1-a-b-cCO 3中的至少一种物质；
其中，0.5≤a≤1，0≤b≤0.5，0≤c≤0.5，M和M'各自独立地选自Al、B、Ba、Ce、Cr、Cu、Fe、K、La、Mg、Mo、Na、Nb、Os、Pr、Re、Ru、Sc、Sr、Sm、Ta、Ti、V、W、Y、Yb、Zn、Zr中的至少一种元素；
所述第一掺杂剂的用量与所述富锂锰基前驱体材料和所述第一掺杂剂的用量之和的摩尔比为0-0.1：1；所述锂盐的用量与所述富锂锰基前驱体材料和所述第一掺杂剂的用量之和的摩尔比为1.0-1.6：1，所述钠盐的用量与所述锂盐的用量的摩尔比为0.005-0.3：1，且所述第一掺杂剂的用量以其中含有的M′元素计，所述富锂锰基前驱体材料的用量以其中含有的Mn、Co、Ni、M元素和计，所述锂盐的用量以其中含有的Li元素计，所述钠盐的用量以其中含有的Na元素计。
本发明的第三方面提供由前述第二方面所述的方法制备得到的富锂锰基材料。
本发明的第四方面提供前述第一方面或第三方面所述的富锂锰基材料在锂 离子电池中的应用。
本发明提供的技术方案与现有技术相比，至少具有如下优点：
1、本发明提供的富锂锰基材料具有优异的循环性能，在电化学循环过程中电压衰减小，结构稳定。
2、本发明提供的富锂锰基材料具有较高的放电比容量、高的首次效率和优异的倍率性能。
3、本发明提供的富锂锰基材料具有比表面积小、振实密度大的优点，有利于降低与电解液之间的副反应，提高电池的体积能量密度。
4、本发明提供的制备方法工艺简单、无污染，掺杂元素和包覆层引入方式简单，过程可控，适合产业化生产。
本发明的其它特征和优点将通过随后的具体实施方式部分予以详细描述。
附图说明
图1是实施例1和对比例1-2制备得到的材料的XRD测试结果图；
图2是实施例1制备得到的富锂锰基材料的扫描电子显微镜图；
图3是对比例1制备得到的基体物质的扫描电子显微镜图；
图4是对比例2制备得到的包覆层物质的扫描电子显微镜图；
图5是实施例1制备得到的富锂锰基材料的首次充放电曲线图；
图6是实施例1制备得到的富锂锰基材料的倍率性能测试结果图；
图7是实施例1和对比例1得到的材料的循环性能测试结果图。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
本发明中，在没有特别说明的情况下，所述室温是指25±2℃。
如前所述，本发明的第一方面提供了一种富锂锰基材料，该富锂锰基材料 含有基体以及包覆在所述基体表面的包覆层；
所述基体中含有化学式为Li 1.2+x[(Mn aCo bNi cM 1-a-b-c) 1-dM′ d] 0.8-xO 2的物质，所述包覆层中含有化学式为Na u[Li v(Mn aCo bNi cM 1-a-b-c) γM′ 1-v-γ]O 2的物质，其中，-0.2≤x≤0.3，0.5≤a≤1，0≤b≤0.5，0≤c≤0.5，0≤d≤0.1，0.4≤u<5/6，0≤v≤0.5，0.5≤γ≤1，M和M'各自独立地选自Al、B、Ba、Ce、Cr、Cu、Fe、K、La、Mg、Mo、Na、Nb、Os、Pr、Re、Ru、Sc、Sr、Sm、Ta、Ti、V、W、Y、Yb、Zn、Zr中的至少一种元素；
在所述材料中，所述包覆层的厚度为10-100nm。
本发明中，所述基体中含有化学式Li 1.2+x[(Mn aCo bNi cM 1-a-b-c) 1-dM′ d] 0.8-xO 2的O3型结构的物质。
本发明中，所述包覆层中含有化学式Na u[Li v(Mn aCo bNi cM 1-a-b-c) γM′ 1-v-γ]O 2的P2型结构物质。
本发明中，所述包覆包括所述包覆层附着在所述基体表面。
优选地，所述富锂锰基材料的中值粒径D50为5-15μm。
优选地，所述富锂锰基材料的比表面积为0.2-8m 2/g，所述富锂锰基材料的振实密度为1.4-2.0g/cm 3。
如前所述，本发明的第二方面提供了一种制备富锂锰基材料的方法，该方法包括：
将富锂锰基前驱体材料与组分A中的各组分进行烧结，得到富锂锰基材料，所述组分A中含有锂盐、钠盐，并且所述组分A中任选还含有第一掺杂剂，所述第一掺杂剂中含有元素M′；
其中，所述富锂锰基前驱体材料选自化学式为Mn aCo bNi cM 1-a-b-c(OH) 2和Mn aCo bNi cM 1-a-b-cCO 3中的至少一种物质；
其中，0.5≤a≤1，0≤b≤0.5，0≤c≤0.5，M和M'各自独立地选自Al、B、Ba、Ce、Cr、Cu、Fe、K、La、Mg、Mo、Na、Nb、Os、Pr、Re、Ru、Sc、Sr、Sm、Ta、Ti、V、W、Y、Yb、Zn、Zr中的至少一种元素；
所述第一掺杂剂的用量与所述富锂锰基前驱体材料和所述第一掺杂剂的用量之和的摩尔比为0-0.1：1；所述锂盐的用量与所述富锂锰基前驱体材料和所述第一掺杂剂的用量之和的摩尔比为1.0-1.6：1，所述钠盐的用量与所述锂盐的用 量的摩尔比为0.005-0.3：1，且所述第一掺杂剂的用量以其中含有的M′元素计，所述富锂锰基前驱体材料的用量以其中含有的Mn、Co、Ni、M元素和计，所述锂盐的用量以其中含有的Li元素计，所述钠盐的用量以其中含有的Na元素计。
在本发明第二方面所述的方法中，所述第一掺杂剂的用量与所述富锂锰基前驱体材料和所述第一掺杂剂的用量之和的摩尔比为0-0.1：1，是指以其中含有的M′元素计的所述第一掺杂剂的用量与以其中含有的Mn、Co、Ni、M元素和计的所述富锂锰基前驱体材料和以其中含有的M′元素计的所述第一掺杂剂的用量之和的摩尔比为0-0.1：1，即为M′/(Ni+Co+Mn+M+M′)＝0-0.1：1。
在本发明第二方面所述的方法中，所述锂盐的用量与所述富锂锰基前驱体材料和所述第一掺杂剂的用量之和的摩尔比为1.0-1.6：1，是指以其中含有的Li元素计的所述锂盐的用量与以其中含有的Mn、Co、Ni、M元素和计的所述富锂锰基前驱体材料和以其中含有的M′元素计的所述第一掺杂剂的用量和的摩尔比为1.0-1.6：1，即为Li/(Ni+Co+Mn+M+M′)＝1.0-1.6：1。
在本发明第二方面所述的方法中，所述钠盐的用量与所述锂盐的用量的摩尔比为0.005-0.3：1，是指以其中含有的钠元素计的所述钠盐的用量与以其中含有的锂元素计的所述锂盐的用量摩尔比为0.005-0.3：1，即为Na/Li＝0.005-0.3：1。
在本发明第二方面所述的方法中，所述锂盐、所述钠盐、所述第一掺杂剂和所述富锂锰基前驱体材料的用量使得得到的富锂锰基材料具有前述第一方面所述的富锂锰基材料的特征。
优选地，根据本发明第二方面所述的方法，所述烧结的条件包括：在含氧气氛或氮气气氛中进行，从室温升温到300-600℃，保温0-6h进行第一烧结，然后继续升温到650-1000℃，保温4-20h进行第二烧结。
根据本发明第二方面所述的方法，当所述第一烧结的保温时间为0时，即没有所述第一烧结，直接从室温升温到650-1000℃，进行所述第二烧结。
优选地，所述锂盐选自碳酸锂、氢氧化锂、氯化锂、硝酸锂、硫酸锂中的至少一种。
优选地，所述钠盐选自碳酸钠、碳酸氢钠、草酸钠、醋酸钠、柠檬酸钠、氯化钠、硝酸钠、硫酸钠、氢氧化钠中的至少一种。
优选地，所述第一掺杂剂选自含有元素M′的氧化物、含有元素M′的磷酸盐、 含有元素M′的氟化物、含有元素M′的碳酸盐中的至少一种。
根据本发明一种优选的具体实施方式，该方法还包括通过以下步骤制备所述富锂锰基前驱体材料：
在溶剂存在下，将组分B中的各组分进行共沉淀反应，得到所述富锂锰基前驱体材料，其中，所述组分B中含有锰盐、沉淀剂和络合剂，并且所述B中任选还含有镍盐、钴盐、第二掺杂剂中的至少一种，所述第二掺杂剂中含有元素M。
其中，所述锰盐、所述沉淀剂、所述络合剂、所述镍盐、所述钴盐、所述第二掺杂剂的用量使得得到的富锂锰基前驱体材料为选自化学式为Mn aCo bNi cM 1-a-b-c(OH) 2和Mn aCo bNi cM 1-a-b-cCO 3中的至少一种物质，其中，0.5≤a≤1，0≤b≤0.5，0≤c≤0.5。
优选地，以其中含有的M元素计的所述第二掺杂剂的用量与其中含有的Ni元素计的所述镍盐、以其中含有的Mn元素计的所述锰盐和以其中含有的Co元素计的所述钴盐的用量和的摩尔比为0-0.1：1，即为M/(Ni+Co+Mn)＝0-0.1：1。
优选地，所述沉淀剂选自氢氧化钠、氢氧化钾、碳酸钠、碳酸钾中的至少一种。当所述沉淀剂为氢氧化钠和/或氢氧化钾时，所述富锂锰基前驱体材料选自化学式为Mn aCo bNi cM 1-a-b-c(OH) 2中的至少一种物质；当所述沉淀剂为碳酸钠和/或碳酸钾时，所述富锂锰基前驱体材料选自化学式为Mn aCo bNi cM 1-a-b-cCO 3中的至少一种物质。
优选地，所述络合剂选自氨水、水杨酸、硫酸铵、氯化铵中的至少一种。
优选地，所述络合剂的浓度为2-10mol/L。
优选地，所述沉淀剂的浓度为4-10mol/L。
本发明中，所述络合剂和所述沉淀剂的用量使得反应体系的pH值为7-12。
优选地，所述第二掺杂剂选自含有元素M的氧化物、含有元素M的磷酸盐、含有元素M的氟化物和含有元素M的碳酸盐中的至少一种。
优选地，所述锰盐、所述钴盐、所述镍盐各自独立地选自其硫酸盐、硝酸盐、氯化物、乙酸盐和柠檬酸盐中的至少一种，例如所述锰盐选自硫酸锰、硝酸锰、氯化锰、乙酸锰、柠檬酸锰中的至少一种；所述钴盐选自硫酸钴、硝酸钴、氯化钴、乙酸钴、柠檬酸钴中的至少一种；所述镍盐选自硫酸镍、硝酸镍、氯化 镍、乙酸镍、柠檬酸镍中的至少一种。
优选地，所述共沉淀反应的条件包括：在反应釜中进行，温度为20-60℃，pH值为7-12、搅拌转速为300-1000rpm，反应时间为10-30h。
以下提供一种更优选的具体实施方式，以说明本发明中所述富锂锰基前驱体材料的制备：
将锰盐和任选存在的镍盐、钴盐、含有元素M的第二掺杂剂中的至少一种溶解得到浓度为1-3mol/L的混合盐溶液，将沉淀剂溶解得到浓度为4-10mol/L的沉淀剂溶液，将络合剂溶解得到浓度为2-10mol/L的络合剂溶液，将所述沉淀剂溶液、所述络合剂溶液、所述混合盐溶液并流加入到反应釜中进行共沉淀反应，所述共沉淀反应的条件包括：温度为20-60℃，pH值为7-12，搅拌转速为300-1000rpm，反应时间为10-30h，得到富锂锰基前驱体材料。
根据本发明另一种优选的具体实施方式，本发明第二方面所述的方法包括：
(1)在溶剂存在下，将组分B中的各组分进行共沉淀反应，得到所述富锂锰基前驱体材料，其中，所述组分B中含有锰盐、沉淀剂和络合剂，并且所述B中任选还含有镍盐、钴盐、第二掺杂剂中的至少一种，所述第二掺杂剂中含有元素M，所述共沉淀反应的条件包括：温度为20-60℃，pH值为7-10，搅拌转速为300-1000rpm，反应时间为10-30h；
(2)将步骤(1)得到的富锂锰基前驱体材料与组分A中的各组分进行烧结，得到富锂锰基材料，所述组分A中含有锂盐、钠盐，并且所述组分A中任选还含有第一掺杂剂，所述第一掺杂剂中含有元素M，所述烧结的条件包括：在含氧气氛或氮气气氛中进行，从室温升温到300-600℃，保温0-6h进行第一烧结，然后继续升温到650-1000℃，保温4-20h进行第二烧结。
本发明第二方面所述的方法还包括抽滤、洗涤、干燥、破碎、筛分等本领域公知的后处理手段，本发明在此不再赘述，本领域技术人员不应理解为对本发明的限制。
如前所述，本发明的第三方面提供了由前述第二方面所述的方法制备得到的富锂锰基材料。
优选地，所述富锂锰基材料包括基体以及包覆在所述基体表面的包覆层，所述基体中含有化学式为Li 1.2+x[(Mn aCo bNi cM 1-a-b-c) 1-dM′ d] 0.8-xO 2的物质，所述包 覆层中含有化学式为Na u[Li v(Mn aCo bNi cM 1-a-b-c) γM′ 1-v-γ]O 2的物质，其中，-0.2≤x≤0.3，0.5≤a≤1，0≤b≤0.5，0≤c≤0.5，0≤d≤0.1，0.4≤u<5/6，0≤v≤0.5，0.5≤γ≤1，M和M'各自独立地选自Al、B、Ba、Ce、Cr、Cu、Fe、K、La、Mg、Mo、Na、Nb、Os、Pr、Re、Ru、Sc、Sr、Sm、Ta、Ti、V、W、Y、Yb、Zn、Zr中的至少一种元素。
优选地，在所述富锂锰基材料中，所述包覆层的厚度为10-100nm。
优选地，所述富锂锰基材料的中值粒径D50为5-15μm。
优选地，所述富锂锰基材料的比表面积为0.2-8m 2/g，所述富锂锰基材料的振实密度为1.4-2.0m 3/g。
本发明中，所述包覆层的容量极低(近似为零)，但是发明人意外地发现，通过在所述基体物质表面原位生成所述包覆层，得到的富锂锰基材料不仅具有优异的倍率性能和循环性能，同时还具有优异的放电比容量。
如前所述，本发明的第四方面提供了前述第一方面或第三方面所述的富锂锰基材料在锂离子电池中的应用。
以下将通过实例对本发明进行详细描述。
以下实例中，在没有特别说明的情况下，所有原料均为市售品。
以下实例中，涉及到的性能是通过以下方式得到的：
(1)物相测试：通过日本理学公司的SmartLab 9kw型号的X射线衍射仪测试得到的；
(2)形貌测试：通过日本日立HITACHI公司的S-4800型号的扫描电子显微镜测试得到的；
(3)中值粒径D 50：通过Marvern公司Hydro 2000mu型号的激光粒度仪测试得到的；
(4)比表面积：通过美国Micromertics公司的Tristar II3020型号的比表面测试仪测试得到的；
(5)振实密度：通过百特公司的BT-30型号的振实密度测试仪测试得到；
(6)电化学性能测试：
以下制备的富锂锰基材料的电化学性能是通过2025型扣式电池测试得到的，具体地：
6.1、2025型扣式电池的制备过程为：
制备极片：将富锂锰基材料、炭黑、聚偏二氟乙烯按质量比为80：10：10与适量的N-甲基吡咯烷酮充分混合形成均匀的浆料，涂覆在铝箔上于120℃烘干、辊压、冲剪，制成直径为11mm的正极片中，所述富锂锰基材料的负载量约为7mg/cm 2。
组装电池：在充有氩气的手套箱内，以锂片为负极，聚丙烯微孔膜为隔膜(Celgard 2400)，1M的LiPF 6/EC+DMC为电解液组装成2025型扣式电池。
6.2、电化学性能测试：
在25℃下，采用新威电池测试系统对2025型扣式电池进行电化学性能测试，其中，1C的充放电电流密度为250mA/g：
a、将制备得到的扣式电池在2.0-4.6V、0.1C下进行充放电测试，评估材料的首次充放电比容量和首次效率；
b、将制备得到的扣式电池在2.0-4.6V、在0.2C下循环100次，评估材料的循环性能和压降；
c、将制备得到的扣式电池在2.0-4.6V、分别在0.1C、0.2C、0.5C、1C下进行充放电测试，评估材料的倍率性能。
实施例1
(1)将硫酸锰、硫酸镍、硫酸钴按照锰、钴、镍元素摩尔比为4：1：1的比例溶解得到浓度为2mol/L的混合盐溶液，将碳酸钠溶解成浓度为2mol/L的沉淀剂溶液；将氨水溶解成浓度为3mol/L的络合剂溶液。将沉淀剂溶液、络合剂溶液、100L的混合盐溶液一起并流加入到反应釜中，在温度为45℃，pH值为8.5，搅拌转速为700rpm下反应20h，然后将浆料经过抽滤、洗涤，滤饼在105℃烘干后筛分，得到富锂锰基材料前驱体材料；
(2)将碳酸锂、碳酸钠和步骤(1)制备得到的富锂锰基材料前驱体材料进行混合均匀，然后在空气气氛中从室温升温至450℃，保温4h进行第一烧结，再升温至850℃，保温10h进行第二烧结，自然冷却，然后经过破碎、筛分，得到富锂锰基材料S1。
在富锂锰基材料S1中，以其中含有的Li元素计的所述碳酸锂的用量与以 其中含有的Ni、Co、Mn元素和计的所述富锂锰基材料前驱体材料的用量摩尔比为Li/(Ni+Co+Mn)＝1.2：1，以其中含有的Na元素计的所述碳酸钠的用量与以其中含有的Li元素计的所述碳酸锂的用量摩尔比为Na/Li＝0.075：1。
实施例2-7
采用与实施例1相似的方式，不同的是：采用的配方或工艺参数不同，其余均与实施例1相同，制备得到富锂锰基材料S2-S7，具体见表1。
表1
Figure PCTCN2021078797-appb-000001
Figure PCTCN2021078797-appb-000002
表1中，在无特别说明的情况下，所述比例和用量比均为摩尔比。
对比例1
采用与实施例1相似的方法，不同的是：在步骤(2)中不加入钠盐，并且以其中含有的Li元素计的所述碳酸锂的用量与以其中含有的Ni、Co、Mn元素和计的所述富锂锰基材料前驱体材料的用量摩尔比为Li/(Ni+Co+Mn)＝1.5：1，制备得到基体材料D1。
对比例2
采用与实施例1相似的方法，不同的是：在步骤(2)中，锂盐和钠盐的加入量不同，具体地：
以其中含有的Li元素计的所述碳酸锂的用量与以其中含有的Ni、Co、Mn元素和计的所述富锂锰基材料前驱体材料的用量摩尔比为Li/(Ni+Co+Mn)＝1：3，以其中含有的Na元素计的所述碳酸钠的用量与以其中含有的Li元素计的所述碳酸锂的用量摩尔比为Na/Li＝10：3。
制备得到包覆层材料D2。
对比例3
采用与实施例1相似的方法，不同的是：在步骤(2)中，锂盐和钠盐的加入量不同，具体地：以其中含有的Li元素计的所述碳酸锂的用量与以其中含有的Ni、Co、Mn元素和计的所述富锂锰基材料前驱体材料的用量摩尔比为Li/(Ni+Co+Mn)＝1：1，以其中含有的Na元素计的所述碳酸钠的用量与以其中含有的Li元素计的所述碳酸锂的用量摩尔比为Na/Li＝0.4：1。
制备得到包覆层厚度约为185nm的富锂锰基材料D3。
对比例4
S1：采用与实施例1相似的方法，不同的是：在实施例1的步骤(2)中不加入钠盐，并且以其中含有的Li元素计的所述碳酸锂的用量与以其中含有的Ni、Co、Mn元素和计的所述富锂锰基材料前驱体材料的用量摩尔比为Li/(Ni+Co+Mn)＝1.5：1，制备得到基体材料D1；
S2：采用与实施例1相似的方法，不同的是：在实施例1的步骤(2)中，锂盐和钠盐的加入量不同，具体地：以其中含有的Li元素计的所述碳酸锂的用量与以其中含有的Ni、Co、Mn元素和计的所述富锂锰基材料前驱体材料的用量摩尔比为Li/(Ni+Co+Mn)＝1：3，以其中含有的Na元素计的所述碳酸钠的用量与以其中含有的Li元素计的所述碳酸锂的用量摩尔比为Na/Li＝10：3，制备得到包覆层材料D2；
S3：将S2制备得到的的包覆层材料D2球磨5h，然后与S1制备的基体材料D1按照重量比为1：10进行混合均匀，然后在空气气氛中从室温升温至450℃，保温4h进行第一烧结，再升温至850℃，保温10h进行第二烧结，自然冷却，然后经过破碎、筛分，得到直接混合烧结制得的富锂锰基材料D4。
制备得到包覆层厚度约为370nm的富锂锰基材料D4。
对比例5
采用与实施例1相似的方法，不同的是：在步骤(2)中，锂盐和钠盐的加入量不同，具体地：以其中含有的Li元素计的所述碳酸锂的用量与以其中含有 的Ni、Co、Mn元素和计的所述富锂锰基材料前驱体材料的用量摩尔比为Li/(Ni+Co+Mn)＝1.6：1，以其中含有的Na元素计的所述碳酸钠的用量与以其中含有的Li元素计的所述碳酸锂的用量摩尔比为Na/Li＝0.075：1。
制备得到包覆层厚度约为50nm的富锂锰基材料D5。
以上实例制备得到的材料的组成，具体如表2所示。
表2
Figure PCTCN2021078797-appb-000003
测试例
(1)XRD测试
本发明测试了以上实例制备得到的富锂锰基材料的XRD，并且示例性地提供了实施例1和对比例1-2的XRD测试结果，如图1所示，从图1中能够看出本发明提供的富锂锰基材料是O3型基体物质和P2型包覆层物质两相的复合结构。
(2)形貌测试
本发明测试了以上实例制备得到的富锂锰基材料的扫描电子显微镜图像，并且示例性地提供了实施例1和对比例1-2的SEM图片，结果分别如图2、图3和图4所示，从图2能够看出本发明提供的富锂锰基材料，包覆层物质成功地对基体物质进行了包覆；从图3能够看出基体物质为一次颗粒形成的二次球形结构； 从图4能够看出包覆层物质也为一次颗粒形成的二次球形结构。
(3)物性测试
本发明测试了以上实例制备得到的富锂锰基材料的中值粒径D 50、振实密度和比表面积，具体结果见表3所示。
表3
实例 中值粒径D 50/μm 振实密度/g/cm 3 比表面积/m 2/g
实施例1 11.9 1.80 6.3
实施例2 10.5 1.88 0.3
实施例3 16.3 1.85 4.8
实施例4 6.8 1.75 0.6
实施例5 9.6 1.82 4.1
实施例6 14.0 1.87 2.4
实施例7 6.2 2.0 1.1
对比例1 10.1 1.70 7.7
对比例2 11.2 1.68 6.5
对比例3 12.0 1.75 6.5
对比例4 12.2 1.65 5.1
对比例5 12.0 1.78 5.8
从表3结果能够看出，本发明提供的富锂锰基材料与其基体材料和包覆层材料相比，具有更高的振实密度和更低的比表面积。
(4)电化学性能测试
本发明测试了以上实例制备得到的材料的电化学性能，包括首次充放电比容量、首次效率、循环性能、倍率性能和压降，具体测试结果见表4。
表4
Figure PCTCN2021078797-appb-000004
注：表4中“\”表示对比例2的平均压降是无法测试的或无测试意义的。
从实施例1和对比例1的结果对比能够看出，本发明提供的富锂锰基材料，与对比例1制备的基体物质相比，在0.1C放电比容量提高了42mAh/g，首次效率提高8％，1C放电比容量提高了39mAh/g，100周的容量保持率提高24％，平均电压衰减减小了140mV，由此可见，本发明提供的富锂锰基材料明显改善了基体物质的性能。
从实施例1和对比例2的结果对比能够看出，本发明提供的包覆层材料的容量极低(近似为零)，但是本发明提供的富锂锰基材料不仅具有优异的倍率性能和循环性能，同时还具有优异的容量性能。
从实施例1和对比例3的结果对比能够看出，本发明提供的富锂锰基材料，与对比例3制备的材料相比，在0.1C放电比容量提高了75mAh/g，首次效率提高15％，1C放电比容量提高了72mAh/g，100周的容量保持率提高3.7％，平均电压衰减减小了20mV，由此可见，特别地要求控制所述包覆层的厚度为10-100nm时，所述富锂锰基材料具有优异的放电比容量、倍率性能和循环性能。
从实施例1和对比例4的结果对比能够看出，本发明提供的富锂锰基材料，与对比例4制备的材料相比，在0.1C放电比容量提高了50mAh/g，首次效率提高12％，1C放电比容量提高了47mAh/g，100周的容量保持率提高18.8％，平均电压衰减减小了50mV，由此可见，本发明提供的制备富锂锰基材料的方法制备得到的富锂锰基材料具有更优异的循环性能、更高的放电比容量。
从实施例1和对比例5的结果对比能够看出，本发明提供的富锂锰基材料，与对比例5制备的材料相比，在0.1C放电比容量提高了44mAh/g，首次效率提高10％，1C放电比容量提高了46mAh/g，100周的容量保持率提高9.8％，平均电压衰减减小了28mV，由此可见，本发明提供的制备富锂锰基材料的方法制备得到的富锂锰基材料具有更优异的循环性能、更高的放电比容量。
本发明示例性地提供了实施例1制备得到的富锂锰基材料的首次充放电曲线测试结果图，如图5所示，从图5能够看出，本发明提供的富锂锰基材料0.1C的放电比容量可达到295mAh/g，首次效率达到94％。
本发明示例性地提供了实施例1制备得到的富锂锰基材料的倍率性能测试结果图，如图6所示，从图6能够看出，本发明提供的富锂锰基材料具有优异的 倍率性能。
本发明示例性地提供了实施例1和对比例1制备的材料的循环性能，如图7所示，从图7可以看出，本发明提供的富锂锰基材料具有优异的循环性能。
由上述结果能够看出，本发明提供的富锂锰基材料具有优异的充放电比容量、高的首效性能、优异的倍率性能和循环性能。特别地，本发明的包覆层材料的放电比容量极低(近似为零)，但是本发明提供的富锂锰基材料不仅具有优异的倍率性能和循环性能，同时还具有优异的放电比容量，其综合性能与其单独的基体材料和包覆层材料相比，都得到了显著地提高。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。

Claims (10)

  1. 一种富锂锰基材料，其特征在于，该富锂锰基材料含有基体以及包覆在所述基体表面的包覆层；
    所述基体中含有化学式为Li 1.2+x[(Mn aCo bNi cM 1-a-b-c) 1-dM′ d] 0.8-xO 2的物质，所述包覆层中含有化学式为Na u[Li v(Mn aCo bNi cM 1-a-b-c) γM′ 1-v-γ]O 2的物质，其中，-0.2≤x≤0.3，0.5≤a≤1，0≤b≤0.5，0≤c≤0.5，0≤d≤0.1，0.4≤u＜5/6，0≤v≤0.5，0.5≤γ≤1，M和M′各自独立地选自Al、B、Ba、Ce、Cr、Cu、Fe、K、La、Mg、Mo、Na、Nb、Os、Pr、Re、Ru、Sc、Sr、Sm、Ta、Ti、V、W、Y、Yb、Zn、Zr中的至少一种元素；
    在所述富锂锰基材料中，所述包覆层的厚度为10-100nm。
  2. 根据权利要求1所述的富锂锰基材料，其中，所述富锂锰基材料的中值粒径D 50为5-15μm；
    优选地，所述富锂锰基材料的比表面积为0.2-8m 2/g，所述富锂锰基材料的振实密度为1.4-2.0g/cm 3。
  3. 一种制备富锂锰基材料的方法，其特征在于，该方法包括：
    将富锂锰基前驱体材料与组分A中的各组分进行烧结，得到富锂锰基材料，所述组分A中含有锂盐、钠盐，并且所述组分A中任选还含有第一掺杂剂，所述第一掺杂剂中含有元素M′；
    所述富锂锰基前驱体材料选自化学式为Mn aCo bNi cM 1-a-b-c(OH) 2 和Mn aCo bNi cM 1-a-b-cCO 3中的至少一种物质；
    其中，0.5≤a≤1，0≤b≤0.5，0≤c≤0.5，M和M′各自独立地选自Al、B、Ba、Ce、Cr、Cu、Fe、K、La、Mg、Mo、Na、Nb、Os、Pr、Re、Ru、Sc、Sr、Sm、Ta、Ti、V、W、Y、Yb、Zn、Zr中的至少一种元素；
    所述第一掺杂剂的用量与所述富锂锰基前驱体材料和所述第一掺杂剂的用量之和的摩尔比为0-0.1∶1；所述锂盐的用量与所述富锂锰基前驱体材料和所述第一掺杂剂的用量之和的摩尔比为1.0-1.6∶1，所述钠盐的用量与所述锂盐的用量的摩尔比为0.005-0.3∶1，且所述第一掺杂剂的用量以其中含有的M′元素计，所述富锂锰基前驱体材料的用量以其中含有的Mn、Co、Ni、M元素和计，所述锂盐的用量以其中含有的Li元素计，所述钠盐的用量以其中含有的Na元素计。
  4. 根据权利要求3所述的方法，其中，所述烧结的条件包括：在含氧气氛或氮气气氛中进行，从室温升温到300-600℃，保温0-6h进行第一烧结，然后继续升温到650-1000℃，保温4-20h进行第二烧结。
  5. 根据权利要求3或4所述的方法，其中，所述锂盐选自碳酸锂、氢氧化锂、氯化锂、硝酸锂、硫酸锂中的至少一种；
    优选地，所述钠盐选自碳酸钠、碳酸氢钠、草酸钠、醋酸钠、柠檬酸钠、氯化钠、硝酸钠、硫酸钠、氢氧化钠中的至少一种；
    优选地，所述第一掺杂剂选自含有元素M′的氧化物、含有元素M′的磷酸盐、含有元素M′的氟化物和含有元素M′的碳酸盐中的至少一种。
  6. 根据权利要求3-5中任意一项所述的方法，其中，该方法还包括通过以下步骤制备所述富锂锰基前驱体材料：
    在溶剂存在下，将组分B中的各组分进行共沉淀反应，得到所述富锂锰基前驱体材料，其中，所述组分B中含有锰盐、沉淀剂和络合剂，并且所述组分B中任选还含有镍盐、钴盐和第二掺杂剂中的至少一种，所述第二掺杂剂中含有元素M。
  7. 根据权利要求6所述的方法，其中，所述沉淀剂选自氢氧化钠、氢氧化钾、碳酸钠、碳酸钾中的至少一种；
    优选地，所述络合剂选自氨水、水杨酸、硫酸铵、氯化铵中的至少一种；
    优选地，所述第二掺杂剂选自含有元素M的氧化物、含有元素M的磷酸盐、含有元素M的氟化物和含有元素M的碳酸盐中的至少一种。
  8. 根据权利要求6或7所述的方法，其中，所述共沉淀反应的条件包括：在反应釜中进行，温度为20-60℃，pH值为7-12，搅拌转速为300-1000rpm，反应时间为10-30h。
  9. 由权利要求3-8中任意一项所述的方法制备得到的富锂锰基材料；
    优选地，所述富锂锰基材料包括基体以及包覆在所述基体表面的包覆层，所述基体中含有化学式为Li 1.2+x[(Mn aCo bNi cM 1-a-b-c) 1-dM′ d] 0.8-xO 2的物质，所述包覆层中含有化学式为Na u[Li v(Mn aCo bNi cM 1-a-b-c) γM′ 1-v-γ]O 2的物质，其中，-0.2≤x≤0.3，0.5≤a≤1，0≤b≤0.5，0≤c≤0.5，0≤d≤0.1，0.4≤u＜5/6，0≤v≤0.5，0.5≤γ≤1，M和M′各自独立地选自Al、B、Ba、Ce、Cr、Cu、Fe、K、La、Mg、Mo、Na、Nb、Os、Pr、Re、Ru、Sc、Sr、Sm、Ta、Ti、V、W、Y、Yb、Zn、Zr中的至少一种元素；
    优选地，在所述富锂锰基材料中，所述包覆层的厚度为10-100nm；
    优选地，所述富锂锰基材料的中值粒径D 50为5-15μm；
    优选地，所述富锂锰基材料的比表面积为0.2-8m 2/g，所述富锂锰基材料的振实密度为1.4-2.0m 3/g。
  10. 权利要求1-2和9中任意一项所述的富锂锰基材料在锂离子电池中的应用。
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