WO2022111186A1 - Lithium iron manganese phosphate composite, preparation method therefor, and lithium-ion battery positive electrode - Google Patents

Lithium iron manganese phosphate composite, preparation method therefor, and lithium-ion battery positive electrode Download PDF

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WO2022111186A1
WO2022111186A1 PCT/CN2021/126398 CN2021126398W WO2022111186A1 WO 2022111186 A1 WO2022111186 A1 WO 2022111186A1 CN 2021126398 W CN2021126398 W CN 2021126398W WO 2022111186 A1 WO2022111186 A1 WO 2022111186A1
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lithium
manganese
phosphate
lithium iron
manganese phosphate
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PCT/CN2021/126398
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French (fr)
Chinese (zh)
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杭道金
陆君
肖天辉
董键
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上海华谊新材料有限公司
上海华谊（集团）公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to a lithium iron manganese phosphate composite material, which is prepared from two different lithium iron manganese phosphate particle materials, and the lithium iron manganese phosphate composite material has high compaction density.
  • the present invention also relates to a method for manufacturing the lithium manganese iron phosphate composite material, a lithium ion battery positive electrode and a lithium ion battery made from the lithium manganese iron phosphate composite material.
  • lithium manganese iron phosphate material is a new type of cathode material for lithium ion batteries. It has the same crystal structure as lithium iron phosphate, and has the characteristics of safety, long life, low cost, and high average voltage, so that its energy density is about 15% higher than that of lithium iron phosphate under the same capacity.
  • the main problems of lithium iron manganese phosphate are its poor electrical conductivity and low compaction density.
  • the current modification methods include nanometerization of materials, bulk doping and surface coating of carbon.
  • the above-mentioned methods, especially the nanometerization and surface carbon coating methods will lead to an increase in the porosity of the lithium manganese iron phosphate material, a decrease in the intrinsic density, and ultimately a low compaction density of the material.
  • CN111710846A discloses an anion-doped lithium manganese iron phosphate material, Li 1+x (Mn 1-yz Fe y M z ) a (PO 4 )(SiO 3 ) b .
  • a silicon-containing lithium iron manganese phosphate precursor is obtained by a one-step method, and then sintered to obtain a highly compacted product.
  • the capacity of the material will be affected to a certain extent, and it is easy to produce impurity phases.
  • CN 111613786 A reported a method for improving compaction density through lithium iron phosphate and lithium manganese iron phosphate composite materials.
  • a blended structure of lithium manganese iron phosphate and lithium iron phosphate is formed, so as to improve the overall compaction density of the material.
  • the lithium iron phosphate contained in the material has a low energy density, so the energy density of the product is low.
  • CN109546140A discloses a method for preparing lithium iron manganese phosphate by water/solvothermal method.
  • the raw material, the solvent and a part of the lithium source are uniformly stirred to form a first suspension
  • the remaining lithium source and the solvent are uniformly stirred to form a second suspension
  • the first suspension and the second suspension are mixed to carry out Solvothermal reaction.
  • the obtained lithium iron manganese phosphate crystal particles are complete, the particle size distribution is narrow, the electrochemical performance is good, and the compaction density is high.
  • the hydrothermal/solvothermal process generates wastewater and the process cost is high.
  • CN109250698A discloses a high tap density lithium manganese iron phosphate positive electrode material and its preparation method and application. Lithium iron manganese is mixed according to the mass ratio of 1 ⁇ 9:9 ⁇ 1, and its tap density is 2.2-2.4g/cm 3 ; the gram capacity is greater than 120mAh/g (123-124.6mAh/g) after 100 cycles at 1C rate .
  • CN109244450A discloses a method for preparing a high-compression and high-capacity lithium manganate composite positive electrode material for blending ternary materials, including preparing small particles of lithium manganate with narrow particle size distribution, and preparing large particles with wide particle size distribution.
  • Lithium manganate after mixing the two, the high-compression and high-capacity lithium manganate composite cathode material of the mixed ternary material is prepared, and the compaction density of the material is above 3.15g/ cm3 (3.15-3.18g) /cm 3 ), 1C gram capacity is 122-125mAh/g.
  • the existing lithium iron manganese phosphate/lithium manganate composites have high compaction density, the compaction density still has room for improvement and requires improved volumetric energy for lithium-ion battery cathode sheets made with such composites density.
  • An inventive object of the present invention is to provide a lithium manganese iron phosphate composite material with improved compaction density and a positive electrode sheet for lithium ion batteries made with the composite material with improved volumetric energy density.
  • one aspect of the present invention relates to a lithium iron manganese phosphate composite material comprising by weight:
  • the primary particle size is 80-500nm
  • the secondary particle size is 5-20 ⁇ m, according to the total moles of metal elements other than lithium in the lithium iron manganese phosphate material In total, the content of manganese in the lithium iron manganese phosphate material is 20-80%;
  • the primary particle size is 30-200nm, and the secondary particle size is 0.5-4 ⁇ m, according to the total moles of metal elements other than lithium in the lithium iron manganese phosphate material In total, the content of manganese in the lithium iron manganese phosphate material is 50-90%;
  • the manganese content of the large particle lithium iron manganese phosphate is lower than that of the small particle lithium manganese iron phosphate.
  • Another aspect of the present invention relates to a kind of preparation method of lithium iron manganese phosphate composite material, and it comprises the steps:
  • a) According to the total weight of the composite material, provide 50-90% large particle lithium iron manganese phosphate, whose primary particle size is 80-500nm, and the secondary particle size is 5-20 ⁇ m, according to the removal of the lithium iron manganese phosphate material.
  • the content of manganese element in the lithium iron manganese phosphate material is 20-80%;
  • the manganese content of the large particle lithium manganese iron phosphate is lower than the manganese content of the small particle lithium manganese iron phosphate
  • Another aspect of the present invention relates to a lithium ion battery positive electrode prepared with the lithium manganese iron phosphate composite material.
  • Yet another aspect of the present invention relates to a lithium ion battery containing the lithium ion battery positive electrode.
  • Fig. 1 is the S4 sample SEM photograph of embodiment 4;
  • Fig. 2 is the S4 sample XRD diffractogram of embodiment 4;
  • FIG. 3 is a charge-discharge curve of sample S4 of Example 4.
  • the lithium iron manganese phosphate composite material of the present invention includes large particles of lithium iron manganese phosphate and small particles of lithium iron manganese phosphate.
  • the lithium iron manganese phosphate composite material of the present invention comprises 50-90% wt, preferably 60-88% wt, more preferably 65-85% wt, preferably 70-80% wt of large particles of lithium iron manganese phosphate.
  • the primary particle size of the lithium iron manganese phosphate large particles of the present invention is 80-500 nm, preferably 100-400 nm; the secondary particle size is 5-20 ⁇ m, preferably 7-15 ⁇ m.
  • the content of manganese element in the lithium iron manganese phosphate large particle material is 20-80%, preferably 40-75%, more preferably 55-65%.
  • the manufacturing method of the large lithium iron manganese phosphate particles is not particularly limited, and can be a conventional method known in the art.
  • the method disclosed in CN104885268A can be used to prepare the large lithium iron manganese phosphate particles.
  • the preparation method of the large lithium iron manganese phosphate particles comprises the following steps: according to a desired ratio, a phosphorus source (such as phosphoric acid), a manganese source (such as manganese oxalate), an iron source (such as suboxalate) Iron), a lithium source (such as lithium carbonate), a carbon source (such as glucose), and a dispersant (such as polyacrylic acid) are added to water, passed through a basket sand mill, and ground into a slurry of a certain particle size, and the slurry is passed through a
  • a phosphorus source such as phosphoric acid
  • a manganese source such as manganese oxalate
  • an iron source such as suboxalate) Iron
  • a lithium source such as lithium carbonate
  • a carbon source such as glucose
  • a dispersant such as polyacrylic acid
  • the lithium iron manganese phosphate composite material of the present invention further comprises 10-50% wt, preferably 12-40% wt of small particles of lithium iron manganese phosphate.
  • the primary particle size of the lithium iron manganese phosphate small particles of the present invention is 30-200 nm, preferably 35-150 nm, more preferably 40-100 nm, preferably 45-80 nm; the secondary particle size is 0.5-4 ⁇ m, preferably 0.8- 3.5 ⁇ m.
  • the content of manganese element in the lithium iron manganese phosphate small particles is 50-90%, preferably 60-88%.
  • the manganese content of the small particle lithium manganese iron phosphate is higher than that of the large particle lithium manganese iron phosphate.
  • the manganese content of the small particles of lithium iron manganese phosphate is at least higher than that of the large particles of lithium iron manganese phosphate. 0.1% higher, preferably at least 0.3% higher, more preferably at least 0.5% higher, preferably at least 0.8% higher, most preferably at least 1.0% higher, preferably at least 1.5% higher.
  • the manganese content of the small particle lithium iron manganese phosphate is higher than the manganese content of the large particle lithium iron manganese phosphate 0.1-35%, preferably 0.3-30% higher, more preferably 0.5-25% higher, preferably 0.8-20% higher, most preferably 1.0-15% higher, preferably 1.2-10% higher.
  • the difference between the manganese content of the small particle lithium iron manganese phosphate and the manganese content of the large particle lithium manganese iron phosphate is calculated as follows: the total number of moles of metal elements other than lithium in the lithium manganese iron phosphate material In total, if the manganese content of small particles of lithium manganese iron phosphate is a%, and the manganese content of large particles of lithium manganese iron phosphate is b%, then the difference between the two is (a-b)%, or the content of small particles of lithium manganese iron phosphate is b%. The manganese content is (a-b)% higher than the manganese content of the large particle lithium manganese iron phosphate.
  • the manufacturing method of the lithium iron manganese phosphate small particles is not particularly limited, and can be a conventional method known in the art.
  • the method disclosed in CN104885268A can be used to prepare the small lithium iron manganese phosphate particles.
  • the preparation method of the small lithium iron manganese phosphate particles includes the following steps: according to a desired ratio, a phosphorus source (such as phosphoric acid), a manganese source (such as manganese oxalate), an iron source (such as suboxalate) Iron), a lithium source (such as lithium carbonate), a carbon source (such as glucose), and a dispersant (such as polyacrylic acid) are added to water, and are ground into a slurry of a certain particle size through a wet bead mill.
  • a phosphorus source such as phosphoric acid
  • a manganese source such as manganese oxalate
  • an iron source such as suboxalate
  • Iron such as lithium carbonate
  • a carbon source such as glucose
  • a dispersant such as polyacrylic acid
  • the method of spray granulation is to prepare secondary particles of a certain particle size, and then sinter in an inert atmosphere, the sintering temperature is 700-750 ° C, and the processing time is 5-10 hours. Pulverize and grind to a certain particle size to obtain the small lithium iron manganese phosphate particles.
  • the lithium iron manganese phosphate composite material of the present invention is a mixture of large particles of lithium iron manganese phosphate with low manganese content and small particles of lithium iron manganese phosphate with high manganese content, wherein the primary particle size of the large particles is larger than the primary particle size of the small particles,
  • the mixing method of the mixture is not particularly limited, and may be a conventional mixing method known in the art. In one example of the present invention, a ball mill jar is used to mix the two into a composite material.
  • the large and small lithium iron manganese phosphate particles both have an olivine crystal structure and belong to the orthorhombic system.
  • the large particles and small particles of lithium iron manganese phosphate are both carbon composite materials, and carbon accounts for 1-3% of the total mass of the respective materials.
  • the overall D50 of the lithium iron manganese phosphate composite material is 3-15 ⁇ m.
  • the particle size distribution of the lithium iron manganese phosphate composite material is a unimodal distribution.
  • the particle size distribution of the lithium iron manganese phosphate composite material is a multimodal distribution.
  • the advantage of the present invention is that,
  • the compacted density of the lithium iron manganese phosphate composite material product of the present invention is high, and the compacted density of the battery pole piece prepared from this product can reach 2.4 g/cm 3 ;
  • the active material is mixed with conductive carbon fiber and binder, and according to the areal density of ⁇ 9mg/ cm2 Coated on one side on aluminum foil and vacuum dried.
  • Test temperature 25 ⁇ 2°C
  • Discharge put at 15mA/g active material, cut off after 2.7V.
  • prepared D50 is a 20-micron lithium manganese iron phosphate material; the XRD test shows that it is a pure-phase lithium manganese iron phosphate material, and the primary particle size is 480 nm according to the Scherrer formula; the carbon content analysis shows that its carbon content is 1.2 %wt.
  • the D50 is 4 microns of lithium manganese iron phosphate material; the XRD test shows that it is a pure phase lithium manganese iron phosphate material, and the primary particle size is 300nm according to the Scherrer formula calculation; the carbon content analysis shows that its carbon content is 1.7%wt.
  • a 4-micron lithium manganese iron phosphate material was prepared, and 100g of the 4-micron lithium manganese iron phosphate material was mixed with 100g BM1-1a, Put it in a ball mill, mix the materials evenly at a speed of 50 rpm, and obtain a uniformly mixed product, denoted as BM1-1b; similarly, on the basis of the formula of BM1-2a, according to the method of BM1-1a, prepare 20-micron phosphoric acid Lithium iron manganese, and take 100g and mix it with 100g BM1-2a, place it in a ball mill, and mix the materials evenly at a rotational speed of 50rpm to obtain a well-mixed product, denoted as BM1-2b;
  • BM 1-2a and b, BM 1-2a and b and S 1 were tested for their compaction density and volumetric energy density according to the preparation method of the pole piece and coin cell previously described. The results are summarized in Table 1.
  • Table 1 The compacted density and volume energy density of the sample of Example 1 and the reference sample
  • Comparative samples BM1-1b and BM1-2b are composites of large particles of lithium manganese iron phosphate and small particles of lithium manganese iron phosphate, but both particles have the same manganese content, resulting in lithium ion batteries made with these composites Has relatively poor pole piece volumetric energy density.
  • the samples BM1-1a and BM1-2a are lithium manganese iron phosphate particles with a single particle size, and the lithium ion batteries prepared by these particles have relatively low pole piece compaction density and pole piece volume energy density.
  • the D50 is 18 micron lithium manganese iron phosphate material; the XRD test shows that it is a pure-phase lithium manganese iron phosphate material, and the primary particle size is 420nm according to the Scherrer formula; the carbon content analysis shows that its carbon content is 1.35%wt.
  • Li:Mn:Fe:P Taking the molar ratio of Li:Mn:Fe:P to be 1.05:0.6:0.4:1.0, adding 8% of the total mass of the above-mentioned materials, glucose, according to the previously described preparation method of the second specification lithium iron manganese phosphate, prepared.
  • D50 is a 3.7-micron lithium manganese iron phosphate material; it is a pure-phase lithium manganese iron phosphate material by XRD test, and the primary particle size is 180 nm according to the Scherrer formula; carbon content analysis shows that its carbon content is 1.9 %wt.
  • each weighed 1200 g of BM 2-1 sample and 800 g of BM 2-2 sample mixed in a high-speed mixer, and rotated at 300 rpm to obtain a uniformly mixed product, denoted as S 2 .
  • BM 2-2, BM 2-2 and S 2 were tested for their compaction density and volumetric energy density according to the preparation method of the pole piece and button battery described previously. The results are summarized in Table 2.
  • Table 2 The compaction density and volume energy density of the sample of Example 2 and the reference sample
  • the D50 is 15 micron lithium manganese iron phosphate material; the XRD test shows that it is a pure phase lithium manganese iron phosphate material, and the primary particle size is 390nm according to the calculation of the Scherrer formula; the carbon content analysis shows that its carbon content is 1.50%wt.
  • D50 is a 2.9-micron lithium manganese iron phosphate material; it is a pure-phase lithium manganese iron phosphate material by XRD test, and the primary particle size is 110 nm according to the Scherrer formula calculation; carbon content analysis shows that its carbon content is 2.1 %wt.
  • each weighed 1400 g of BM 2-1 sample and 600 g of BM 2-2 sample mixed in a high-speed mixer, and rotated at 300 rpm to obtain a uniformly mixed product, which was denoted as S 3 .
  • Table 3 The compacted density and volume energy density of the sample of Example 3 and the reference sample
  • the D50 is 12 micron lithium manganese iron phosphate material; the XRD test shows that it is a pure phase lithium manganese iron phosphate material, and the primary particle size is 310nm according to the Scherrer formula calculation; the carbon content analysis shows that its carbon content is 1.8%wt.
  • D50 is a 2.3-micron lithium manganese iron phosphate material; after XRD test, it is a pure phase lithium manganese iron phosphate material, and the primary particle size is 80nm according to Scherrer formula calculation; carbon content analysis shows that its carbon content is 2.3 %wt.
  • BM 4-1, BM 4-2 and S 4 were tested for their compaction density and volumetric energy density according to the preparation method of the pole piece and button battery described previously. The results are summarized in Table 4.
  • Figure 1 Figure 1 and Figure 3 are the SEM image, XRD image and charge-discharge curve diagram of the S4 sample of Example 4, respectively.
  • Table 4 The compacted density and volume energy density of the sample of Example 4 and the reference sample
  • BM 4-1 BM 4-2 S 4 Pole piece compaction density (g/cm 3 ) 2.28 1.78 2.42 Pole Piece Volume Energy Density (Wh/cm 3 ) 1.20 1.01 1.32
  • the D50 is 10 micron lithium manganese iron phosphate material; the XRD test shows that it is a pure-phase lithium manganese iron phosphate material, and the primary particle size is 260nm according to the Scherrer formula calculation; the carbon content analysis shows that its carbon content is 2.1%wt.
  • D50 is a 1.7-micron lithium manganese iron phosphate material; it is a pure-phase lithium manganese iron phosphate material by XRD test, and the primary particle size is 60nm according to the Scherrer formula calculation; carbon content analysis shows that its carbon content is 2.9 %wt.
  • BM 5-1, BM 5-2 and S 5 were tested for their compaction density and volumetric energy density according to the preparation method of the pole piece and button battery described previously. The results are summarized in Table 5.
  • Table 5 The compacted density and volume energy density of the sample of Example 5 and the reference sample
  • the D50 is 8 microns lithium manganese iron phosphate material; the XRD test shows that it is a pure-phase lithium manganese iron phosphate material, and the primary particle size is 260 nm according to the Scherrer formula; the carbon content analysis shows that its carbon content is 2.3%wt.
  • each weighed 1600 g of BM 6-1 sample and 400 g of BM 6-2 sample mixed in a high-speed mixer, and rotated at 300 rpm to obtain a well-mixed product, denoted as S 6.
  • BM 6-1, BM 6-2 and S 6 were tested for their compaction density and volumetric energy density according to the preparation method of the pole piece and button battery described previously. The results are summarized in Table 6.
  • Table 6 The compacted density and volume energy density of the sample of Example 6 and the reference sample
  • the D50 is 5 microns lithium manganese iron phosphate material; the XRD test shows that it is a pure phase lithium manganese iron phosphate material, and the primary particle size is 80 nm according to the calculation of Scherrer formula; the carbon content analysis shows that its carbon content is 2.8%wt.
  • lithium iron manganese phosphate to prepare D50 is a 0.8-micron lithium manganese iron phosphate material; it is a pure-phase lithium manganese iron phosphate material by XRD test, and the primary particle size is 39nm according to the Scherrer formula; the carbon content analysis shows that its carbon content is 2.9 %wt.
  • BM 7-1, BM 7-2 and S 7 were tested for their compaction density and volumetric energy density according to the preparation method of the pole piece and button battery described previously. The results are summarized in Table 7.
  • Table 7 The compacted density and volume energy density of the sample of Example 7 and the reference sample

Abstract

Disclosed are a lithium iron manganese phosphate composite, a preparation method therefor, and a lithium-ion battery positive electrode. By weight, the lithium iron manganese phosphate composite material comprises: a) 50-90% of large-particle lithium iron manganese phosphate, the primary particle size thereof being 80-500 nm, the secondary particle size thereof being 5-20 μm, and the content of the manganese element in the lithium iron manganese phosphate material being 20-80% based on the total number of moles of transition metal elements in the lithium iron manganese phosphate material; and b) 10-50% of small-particle lithium iron manganese phosphate, the primary particle size thereof being 30-200 nm, the secondary particle size thereof being 0.5-4 μm, and the content of the manganese element in the lithium iron manganese phosphate material being 50-90% based on the total number of moles of transition metal elements in the lithium iron manganese phosphate material, the manganese content in the large-particle lithium iron manganese phosphate being lower than the manganese content in the small-particle lithium iron manganese phosphate.

Description

磷酸锰铁锂复合物，其制造方法及锂离子电池正极Lithium iron manganese phosphate composite, method for producing the same, and positive electrode for lithium ion battery 技术领域technical field
本发明涉及一种磷酸锰铁锂复合材料，它是由两种不同的磷酸锰铁锂颗粒材料制得，这种磷酸锰铁锂复合材料具有高的压实密度。本发明还涉及所述磷酸锰铁锂复合材料的制造方法和用该磷酸锰铁锂复合材料制得的锂离子电池正极以及锂离子电池。The invention relates to a lithium iron manganese phosphate composite material, which is prepared from two different lithium iron manganese phosphate particle materials, and the lithium iron manganese phosphate composite material has high compaction density. The present invention also relates to a method for manufacturing the lithium manganese iron phosphate composite material, a lithium ion battery positive electrode and a lithium ion battery made from the lithium manganese iron phosphate composite material.
技术背景technical background
作为磷酸铁锂的类质同晶物，磷酸锰铁锂材料是一种锂离子电池的新型正极材料。其具有和磷酸铁锂相同的晶体结构，均具有安全、长寿命、低成本的特点，并且平均电压高，使其在相同容量下，其能量密度要比磷酸铁锂高15％左右。As an isomorph of lithium iron phosphate, lithium manganese iron phosphate material is a new type of cathode material for lithium ion batteries. It has the same crystal structure as lithium iron phosphate, and has the characteristics of safety, long life, low cost, and high average voltage, so that its energy density is about 15% higher than that of lithium iron phosphate under the same capacity.
目前磷酸锰铁锂存在的主要问题，是其较差的导电性和较低的压实密度。针对其导电性差的弊端，目前的改性手段包括，材料的纳米化，体相掺杂和表面包覆碳等工艺。然而上述手段，尤其是纳米化和表面包碳手段，会导致磷酸锰铁锂材料的孔隙率增多，本征密度下降，最终导致材料的压实密度偏低。At present, the main problems of lithium iron manganese phosphate are its poor electrical conductivity and low compaction density. In view of the disadvantages of its poor conductivity, the current modification methods include nanometerization of materials, bulk doping and surface coating of carbon. However, the above-mentioned methods, especially the nanometerization and surface carbon coating methods, will lead to an increase in the porosity of the lithium manganese iron phosphate material, a decrease in the intrinsic density, and ultimately a low compaction density of the material.
磷酸锰铁锂材料的制备手段以及压实密度的提升手段，目前有如下报道。The preparation methods of lithium manganese iron phosphate materials and the methods for improving the compaction density are currently reported as follows.
CN111710846A公开了一种阴离子掺杂型的磷酸锰铁锂材料，Li 1+x(Mn 1-y-zFe yM z) a(PO 4)(SiO 3) b。该专利通过一步法得到了含硅的磷酸锰铁锂前驱体，然后烧结得到了高压实的产物。但是由于硅的存在，材料的容量等会受到一定的影响，并且容易生产杂相。 CN111710846A discloses an anion-doped lithium manganese iron phosphate material, Li 1+x (Mn 1-yz Fe y M z ) a (PO 4 )(SiO 3 ) b . In this patent, a silicon-containing lithium iron manganese phosphate precursor is obtained by a one-step method, and then sintered to obtain a highly compacted product. However, due to the presence of silicon, the capacity of the material will be affected to a certain extent, and it is easy to produce impurity phases.
CN 111613786 A报道了通过磷酸铁锂和磷酸锰铁锂复合材料，改善压实密度的方法。通过制备磷酸锰铁和磷酸铁，然后共混后造粒烧结，形成磷酸锰铁锂和磷酸铁锂共混的结构，以此提高材料整体的压实密度。然而材料中所含有的磷酸铁锂能量密度较低，因而产物的能量密度偏低。CN 111613786 A reported a method for improving compaction density through lithium iron phosphate and lithium manganese iron phosphate composite materials. By preparing ferric manganese phosphate and ferric phosphate, and then granulating and sintering after blending, a blended structure of lithium manganese iron phosphate and lithium iron phosphate is formed, so as to improve the overall compaction density of the material. However, the lithium iron phosphate contained in the material has a low energy density, so the energy density of the product is low.
CN109546140A公开了一种水/溶剂热法制备磷酸锰铁锂的方法。该方法将原料、溶剂以及部分锂源搅拌均匀形成第一悬浊液，将剩余锂源和溶剂搅拌均匀形成第二悬浊液，再将第一悬浊液和第二悬浊液混合，进行溶剂热反应。所得磷酸锰铁锂晶体颗粒完整，粒径分布窄，电化学性能好，压实密度较高。然而水热/溶剂热过程会产生废水，并且工艺成本较高。CN109546140A discloses a method for preparing lithium iron manganese phosphate by water/solvothermal method. In the method, the raw material, the solvent and a part of the lithium source are uniformly stirred to form a first suspension, the remaining lithium source and the solvent are uniformly stirred to form a second suspension, and then the first suspension and the second suspension are mixed to carry out Solvothermal reaction. The obtained lithium iron manganese phosphate crystal particles are complete, the particle size distribution is narrow, the electrochemical performance is good, and the compaction density is high. However, the hydrothermal/solvothermal process generates wastewater and the process cost is high.
CN109250698A公开了一种高振实密度磷酸锰铁锂正极材料及其制备方法和应用，所述正极材料由粒径为0.3-0.8μm的小颗粒磷酸锰铁锂和粒径为3-5μm的大颗粒磷酸锰铁锂按质量比1～9：9～1混合而成，其振实密度为2.2-2.4g/cm 3；1C倍率循环100圈后克容量大于120mAh/g(123-124.6mAh/g)。 CN109250698A discloses a high tap density lithium manganese iron phosphate positive electrode material and its preparation method and application. Lithium iron manganese is mixed according to the mass ratio of 1～9:9～1, and its tap density is 2.2-2.4g/cm 3 ; the gram capacity is greater than 120mAh/g (123-124.6mAh/g) after 100 cycles at 1C rate .
CN109244450A公开了一种用于掺混三元材料的高压实高容量型锰酸锂复合正极材料的制备方法，包括制备小颗粒窄粒径分布的锰酸锂，制备大颗粒宽粒径分布的锰酸锂，将两者混合后制得所述掺混三元材料的高压实高容量型锰酸锂复合正极材料，该材料的压实密度为3.15g/cm 3以上(3.15-3.18g/cm 3)，1C克容量为122-125mAh/g。 CN109244450A discloses a method for preparing a high-compression and high-capacity lithium manganate composite positive electrode material for blending ternary materials, including preparing small particles of lithium manganate with narrow particle size distribution, and preparing large particles with wide particle size distribution. Lithium manganate, after mixing the two, the high-compression and high-capacity lithium manganate composite cathode material of the mixed ternary material is prepared, and the compaction density of the material is above 3.15g/ cm3 (3.15-3.18g) /cm 3 ), 1C gram capacity is 122-125mAh/g.
尽管现有的磷酸锰铁锂/锰酸锂复合材料具有高的压实密度，但是压实密度仍具有改进的余地并且要求用这种复合材料制得的锂离子电池正极片具有改进的体积能量密度。Although the existing lithium iron manganese phosphate/lithium manganate composites have high compaction density, the compaction density still has room for improvement and requires improved volumetric energy for lithium-ion battery cathode sheets made with such composites density.
发明内容SUMMARY OF THE INVENTION
本发明的一个发明目的是提供一种磷酸锰铁锂复合材料，它具有改进的压实密度并且用这种复合材料制得的锂离子电池正极片具有改进的体积能量密度。An inventive object of the present invention is to provide a lithium manganese iron phosphate composite material with improved compaction density and a positive electrode sheet for lithium ion batteries made with the composite material with improved volumetric energy density.
因此，本发明的一个方面涉及一种磷酸锰铁锂复合材料，以重量计它包括：Accordingly, one aspect of the present invention relates to a lithium iron manganese phosphate composite material comprising by weight:
a)50-90％大颗粒磷酸锰铁锂，其一次粒径为80-500nm，二次粒径为5-20μm，按所述磷酸锰铁锂材料中除锂以外的金属元素的总摩尔数计，磷酸锰铁锂材料中锰元素的含量为20-80％；a) 50-90% large particle lithium iron manganese phosphate, the primary particle size is 80-500nm, and the secondary particle size is 5-20μm, according to the total moles of metal elements other than lithium in the lithium iron manganese phosphate material In total, the content of manganese in the lithium iron manganese phosphate material is 20-80%;
b)10-50％小颗粒磷酸锰铁锂，其一次粒径为30-200nm，二次粒径为0.5-4μm，按所述磷酸锰铁锂材料中除锂以外的金属元素的总摩尔数计，磷酸锰铁锂材料中锰元素的含量为50-90％；b) 10-50% small particle lithium iron manganese phosphate, the primary particle size is 30-200nm, and the secondary particle size is 0.5-4 μm, according to the total moles of metal elements other than lithium in the lithium iron manganese phosphate material In total, the content of manganese in the lithium iron manganese phosphate material is 50-90%;
所述大颗粒磷酸锰铁锂的锰含量要低于所述小颗粒磷酸锰铁锂的锰含量。The manganese content of the large particle lithium iron manganese phosphate is lower than that of the small particle lithium manganese iron phosphate.
本发明的另一方面涉及一种磷酸锰铁锂复合材料的制备方法，它包括如下步骤：Another aspect of the present invention relates to a kind of preparation method of lithium iron manganese phosphate composite material, and it comprises the steps:
a)按复合材料的总重量计，提供50-90％大颗粒磷酸锰铁锂，其一次粒径为80-500nm，二次粒径为5-20μm，按所述磷酸锰铁锂材料中除锂以外的金属元素的总摩尔数计，磷酸锰铁锂材料中锰元素的含量为20-80％；a) According to the total weight of the composite material, provide 50-90% large particle lithium iron manganese phosphate, whose primary particle size is 80-500nm, and the secondary particle size is 5-20μm, according to the removal of the lithium iron manganese phosphate material. In terms of the total moles of metal elements other than lithium, the content of manganese element in the lithium iron manganese phosphate material is 20-80%;
b)提供10-50％小颗粒磷酸锰铁锂，其一次粒径为30-200nm，二次粒径为0.5-4μm，按所述磷酸锰铁锂材料中除锂以外的金属元素的总摩尔数计，磷酸锰铁锂材料中锰元素的含量为50-90％；b) Provide 10-50% small particle lithium iron manganese phosphate with a primary particle size of 30-200 nm and a secondary particle size of 0.5-4 μm, according to the total moles of metal elements other than lithium in the lithium iron manganese phosphate material In terms of numbers, the content of manganese in the lithium iron manganese phosphate material is 50-90%;
其中，所述大颗粒磷酸锰铁锂的锰含量要低于所述小颗粒磷酸锰铁锂的锰含量； 和Wherein, the manganese content of the large particle lithium manganese iron phosphate is lower than the manganese content of the small particle lithium manganese iron phosphate; and
c)混合所述大颗粒磷酸锰铁锂和所述小颗粒磷酸锰铁锂。c) Mixing the large particles of lithium iron manganese phosphate and the small particles of lithium iron manganese phosphate.
本发明的另一方面涉及用所述磷酸锰铁锂复合材料制得的锂离子电池正极。Another aspect of the present invention relates to a lithium ion battery positive electrode prepared with the lithium manganese iron phosphate composite material.
本发明的再一方面涉及含有所述锂离子电池正极的锂离子电池。Yet another aspect of the present invention relates to a lithium ion battery containing the lithium ion battery positive electrode.
附图说明Description of drawings
下面结合附图进一步说明本发明。附图中：The present invention will be further described below in conjunction with the accompanying drawings. In the attached picture:
图1是实施例4的S4样品SEM照片；Fig. 1 is the S4 sample SEM photograph of embodiment 4;
图2是实施例4的S4样品XRD衍射图；Fig. 2 is the S4 sample XRD diffractogram of embodiment 4;
图3是实施例4的样品S4的充放电曲线。FIG. 3 is a charge-discharge curve of sample S4 of Example 4. FIG.
具体实施方式Detailed ways
本发明磷酸锰铁锂复合材料包括大颗粒磷酸锰铁锂颗粒和小颗粒磷酸锰铁锂颗粒。The lithium iron manganese phosphate composite material of the present invention includes large particles of lithium iron manganese phosphate and small particles of lithium iron manganese phosphate.
a)磷酸锰铁锂大颗粒a) Large particles of lithium iron manganese phosphate
本发明磷酸锰铁锂复合材料包括50-90％wt，较好60-88％wt，更好65-85％wt，优选70-80％wt的磷酸锰铁锂大颗粒。The lithium iron manganese phosphate composite material of the present invention comprises 50-90% wt, preferably 60-88% wt, more preferably 65-85% wt, preferably 70-80% wt of large particles of lithium iron manganese phosphate.
本发明磷酸锰铁锂大颗粒的一次粒径为80-500nm，较好为100-400nm；二次粒径为5-20μm，较好为7-15μm，。The primary particle size of the lithium iron manganese phosphate large particles of the present invention is 80-500 nm, preferably 100-400 nm; the secondary particle size is 5-20 μm, preferably 7-15 μm.
按所述磷酸锰铁锂材料中除锂以外的金属元素的总摩尔数计，所述磷酸锰铁锂大颗粒材料中锰元素的含量为20-80％，优选40-75％，更优为55-65％。According to the total moles of metal elements other than lithium in the lithium iron manganese phosphate material, the content of manganese element in the lithium iron manganese phosphate large particle material is 20-80%, preferably 40-75%, more preferably 55-65%.
所述磷酸锰铁锂大颗粒的制造方法无特别的限制，可以是本领域已知的常规方法。例如，可采用CN104885268A公开的方法制备所述磷酸锰铁锂大颗粒。The manufacturing method of the large lithium iron manganese phosphate particles is not particularly limited, and can be a conventional method known in the art. For example, the method disclosed in CN104885268A can be used to prepare the large lithium iron manganese phosphate particles.
在本发明的一个实例中，所述磷酸锰铁锂大颗粒的制备方法包括如下步骤：按照所需配比将磷源(例如磷酸)、锰源(例如草酸锰)、铁源(例如草酸亚铁)、锂源(例如碳酸锂)、碳源(例如葡萄糖)以及分散剂(例如聚丙烯酸)加到水中，通过篮式砂磨机，研磨成一定粒径的浆料，将该浆料通过喷雾造粒的方法，制备成预定粒径的二次颗粒，然后在惰性气氛中烧结，烧结温度700-750℃，处理时间5-10小时，得到所述磷酸锰铁锂大颗粒。In an example of the present invention, the preparation method of the large lithium iron manganese phosphate particles comprises the following steps: according to a desired ratio, a phosphorus source (such as phosphoric acid), a manganese source (such as manganese oxalate), an iron source (such as suboxalate) Iron), a lithium source (such as lithium carbonate), a carbon source (such as glucose), and a dispersant (such as polyacrylic acid) are added to water, passed through a basket sand mill, and ground into a slurry of a certain particle size, and the slurry is passed through a In the method of spray granulation, secondary particles of predetermined particle size are prepared, and then sintered in an inert atmosphere, the sintering temperature is 700-750° C., and the treatment time is 5-10 hours to obtain the large lithium iron manganese phosphate particles.
b)磷酸锰铁锂小颗粒b) Small Lithium Iron Manganese Phosphate Particles
本发明磷酸锰铁锂复合材料还包括10-50％wt，较好12-40％wt的磷酸锰铁锂小颗粒。The lithium iron manganese phosphate composite material of the present invention further comprises 10-50% wt, preferably 12-40% wt of small particles of lithium iron manganese phosphate.
本发明磷酸锰铁锂小颗粒的一次粒径为30-200nm，较好为35-150nm，更好为40-100nm，优选45-80nm；二次粒径为0.5-4μm，较好为0.8-3.5μm。The primary particle size of the lithium iron manganese phosphate small particles of the present invention is 30-200 nm, preferably 35-150 nm, more preferably 40-100 nm, preferably 45-80 nm; the secondary particle size is 0.5-4 μm, preferably 0.8- 3.5μm.
按所述磷酸锰铁锂材料中除锂以外的金属元素总摩尔数计，所述磷酸锰铁锂小颗粒中锰元素的含量为50-90％、较好为60-88％。Based on the total moles of metal elements other than lithium in the lithium iron manganese phosphate material, the content of manganese element in the lithium iron manganese phosphate small particles is 50-90%, preferably 60-88%.
在本发明中，所述小颗粒磷酸锰铁锂的锰含量要高于大颗粒磷酸锰铁锂的锰含量。在本发明的一个实例中，按所述磷酸锰铁锂材料中除锂以外的金属元素总摩尔数计，所述小颗粒磷酸锰铁锂的锰含量比大颗粒磷酸锰铁锂的锰含量至少高0.1％，较好至少高0.3％，更好至少高0.5％，宜至少高0.8％，最好至少高1.0％，优选至少高1.5％。In the present invention, the manganese content of the small particle lithium manganese iron phosphate is higher than that of the large particle lithium manganese iron phosphate. In an example of the present invention, in terms of the total moles of metal elements other than lithium in the lithium iron manganese phosphate material, the manganese content of the small particles of lithium iron manganese phosphate is at least higher than that of the large particles of lithium iron manganese phosphate. 0.1% higher, preferably at least 0.3% higher, more preferably at least 0.5% higher, preferably at least 0.8% higher, most preferably at least 1.0% higher, preferably at least 1.5% higher.
在本发明的一个实例中，按所述磷酸锰铁锂材料中除锂以外的金属元素总摩尔数计，所述小颗粒磷酸锰铁锂的锰含量比大颗粒磷酸锰铁锂的锰含量高0.1-35％，较好高0.3-30％，更好高0.5-25％，宜高0.8-20％，最好高1.0-15％，优选高1.2-10％。In an example of the present invention, in terms of the total moles of metal elements other than lithium in the lithium iron manganese phosphate material, the manganese content of the small particle lithium iron manganese phosphate is higher than the manganese content of the large particle lithium iron manganese phosphate 0.1-35%, preferably 0.3-30% higher, more preferably 0.5-25% higher, preferably 0.8-20% higher, most preferably 1.0-15% higher, preferably 1.2-10% higher.
在本发明中，所述小颗粒磷酸锰铁锂的锰含量与大颗粒磷酸锰铁锂的锰含量的差值是这样计算的：以磷酸锰铁锂材料中除锂以外的金属元素总摩尔数计，若小颗粒磷酸锰铁锂的锰含量为a％,大颗粒磷酸锰铁锂的锰含量为b％，则两者的差值为(a-b)％，或者说小颗粒磷酸锰铁锂的锰含量比大颗粒磷酸锰铁锂的锰含量高(a-b)％。In the present invention, the difference between the manganese content of the small particle lithium iron manganese phosphate and the manganese content of the large particle lithium manganese iron phosphate is calculated as follows: the total number of moles of metal elements other than lithium in the lithium manganese iron phosphate material In total, if the manganese content of small particles of lithium manganese iron phosphate is a%, and the manganese content of large particles of lithium manganese iron phosphate is b%, then the difference between the two is (a-b)%, or the content of small particles of lithium manganese iron phosphate is b%. The manganese content is (a-b)% higher than the manganese content of the large particle lithium manganese iron phosphate.
同样，所述磷酸锰铁锂小颗粒的制造方法无特别的限制，可以是本领域已知的常规方法。例如，可采用CN104885268A公开的方法制备所述磷酸锰铁锂小颗粒。Likewise, the manufacturing method of the lithium iron manganese phosphate small particles is not particularly limited, and can be a conventional method known in the art. For example, the method disclosed in CN104885268A can be used to prepare the small lithium iron manganese phosphate particles.
在本发明的一个实例中，所述磷酸锰铁锂小颗粒的制备方法包括如下步骤：按照所需配比将磷源(例如磷酸)、锰源(例如草酸锰)、铁源(例如草酸亚铁)、锂源(例如碳酸锂)、碳源(例如葡萄糖)以及分散剂(例如聚丙烯酸)加到水中，通过湿法珠磨机，研磨成一定粒径的浆料，将该浆料通过喷雾造粒的方法，制备成一定粒径的二次颗粒，然后在惰性气氛中烧结，烧结温度700-750℃，处理时间5-10小时，再将粉末取出，通过高能球磨或气流粉碎或机械粉碎，研磨到一定的粒径，得到所述磷酸锰铁锂小颗粒。In an example of the present invention, the preparation method of the small lithium iron manganese phosphate particles includes the following steps: according to a desired ratio, a phosphorus source (such as phosphoric acid), a manganese source (such as manganese oxalate), an iron source (such as suboxalate) Iron), a lithium source (such as lithium carbonate), a carbon source (such as glucose), and a dispersant (such as polyacrylic acid) are added to water, and are ground into a slurry of a certain particle size through a wet bead mill. The method of spray granulation is to prepare secondary particles of a certain particle size, and then sinter in an inert atmosphere, the sintering temperature is 700-750 ° C, and the processing time is 5-10 hours. Pulverize and grind to a certain particle size to obtain the small lithium iron manganese phosphate particles.
本发明磷酸锰铁锂复合材料是低锰含量的磷酸锰铁锂大颗粒和高锰含量的磷酸锰铁锂小颗粒的混合物，其中大颗粒的一次粒径大于所述小颗粒的一次粒径， 所述混合物的混合方法无特别的限制，可以是本领域已知的常规混合方法。在本发明的一个实例中，采用球磨罐将两者混合成复合材料。The lithium iron manganese phosphate composite material of the present invention is a mixture of large particles of lithium iron manganese phosphate with low manganese content and small particles of lithium iron manganese phosphate with high manganese content, wherein the primary particle size of the large particles is larger than the primary particle size of the small particles, The mixing method of the mixture is not particularly limited, and may be a conventional mixing method known in the art. In one example of the present invention, a ball mill jar is used to mix the two into a composite material.
在本发明的一个实例中，所述磷酸锰铁锂大颗粒和小颗粒均具有的橄榄石晶体结构，属于正交晶系。In an example of the present invention, the large and small lithium iron manganese phosphate particles both have an olivine crystal structure and belong to the orthorhombic system.
在本发明的一个实例中，所述磷酸锰铁锂大颗粒和小颗粒均为碳复合材料，碳占各自材料总质量的1-3％。In an example of the present invention, the large particles and small particles of lithium iron manganese phosphate are both carbon composite materials, and carbon accounts for 1-3% of the total mass of the respective materials.
在本发明的一个实例中，所述磷酸锰铁锂复合材料整体的D50为3-15μm。In an example of the present invention, the overall D50 of the lithium iron manganese phosphate composite material is 3-15 μm.
在本发明的一个实例中，所述磷酸锰铁锂复合材料的粒径分布为单峰分布。In an example of the present invention, the particle size distribution of the lithium iron manganese phosphate composite material is a unimodal distribution.
在本发明的一个实例中，所述磷酸锰铁锂复合材料的粒径分布为多峰分布。In an example of the present invention, the particle size distribution of the lithium iron manganese phosphate composite material is a multimodal distribution.
本发明的优势在于，The advantage of the present invention is that,
(i)本发明所涉及的复合磷酸锰铁锂，其制备方法简单，在传统制备工艺上，只需要按照配比物理混合，即可得到所需要的产物；(i) the composite lithium iron manganese phosphate involved in the present invention, its preparation method is simple, in the traditional preparation technology, only needs to be physically mixed according to the proportioning, and the required product can be obtained;
(ii)本发明磷酸锰铁锂复合材料产品的压实密度高，由本产品制备成的电池极片，其压实密度可以达到2.4g/cm 3； (ii) the compacted density of the lithium iron manganese phosphate composite material product of the present invention is high, and the compacted density of the battery pole piece prepared from this product can reach 2.4 g/cm 3 ;
(iii)本发明，其产品能量密度高。(iii) In the present invention, its products have high energy density.
实施例Example
以下，结合具体实施例，进一步对本发明的内容进行说明。Hereinafter, the content of the present invention will be further described with reference to specific embodiments.
1.所得磷酸锰铁锂的电化学性能测试方法：1. The electrochemical performance test method of the gained lithium manganese iron phosphate:
按照活性物质：导电剂：粘结剂＝94:3:3的重量比例，并辅以NMP作为溶剂，将活性物质和导电炭纤维及粘结剂混合，并按照～9mg/cm 2的面密度单面涂布在铝箔上并真空干燥。将干燥完的极片进行辊压，并根据辊压后的极片厚度，以及面密度，极片切圆后，以锂片为对电极，六氟合磷酸锂浓度为1.0M，DMC:EC＝1:1(V/V)的溶液为电解液，20微米厚的PP隔膜隔离正负极，组装成CR2025扣式电池。按照如下条件进行倍率测试： According to the weight ratio of active material: conductive agent: binder = 94:3:3, and supplemented with NMP as a solvent, the active material is mixed with conductive carbon fiber and binder, and according to the areal density of ~9mg/ cm2 Coated on one side on aluminum foil and vacuum dried. Roll the dried pole piece, and according to the thickness and surface density of the pole piece after rolling, after the pole piece is cut into a circle, the lithium piece is used as the counter electrode, the concentration of lithium hexafluorophosphate is 1.0M, DMC:EC The solution of =1:1(V/V) is the electrolyte, and the positive and negative electrodes are separated by a 20-micron-thick PP diaphragm, which is assembled into a CR2025 button battery. Carry out the magnification test according to the following conditions:
测试温度：25±2℃；Test temperature: 25±2℃;
电压范围：2.7-4.25V；Voltage range: 2.7-4.25V;
测试流程：Test process:
充电：按150mA/g充，4.25V后1.5mA/g恒压截止；Charging: Charge at 150mA/g, 1.5mA/g constant voltage cut off after 4.25V;
放电：按15mA/g活性物质放，2.7V后截止。Discharge: put at 15mA/g active material, cut off after 2.7V.
实施例1Example 1
1.磷酸锰铁锂大颗粒(记为BM 1-1a)的制备：1. Preparation of Lithium Iron Manganese Phosphate Large Particles (denoted as BM 1-1a):
以Li:Mn:Fe:P的摩尔比例为1.03:0.2:0.8:1.0的比例，加入上述物料总质量的约5％的葡萄糖，按照先前所述磷酸锰铁锂大颗粒的制备方法，制备出D50为20微米的磷酸锰铁锂材料；经XRD测试，其为纯相的磷酸锰铁锂材料，并结合谢乐公式计算，其一次颗粒尺寸为480nm；碳含量分析显示，其碳含量为1.2％wt。Taking the molar ratio of Li:Mn:Fe:P to be 1.03:0.2:0.8:1.0, adding about 5% of the total mass of the above-mentioned material glucose, according to the previously described preparation method of lithium iron manganese phosphate large particles, prepared D50 is a 20-micron lithium manganese iron phosphate material; the XRD test shows that it is a pure-phase lithium manganese iron phosphate material, and the primary particle size is 480 nm according to the Scherrer formula; the carbon content analysis shows that its carbon content is 1.2 %wt.
2.磷酸锰铁锂小颗粒(记为BM 1-2a)的制备：2. Preparation of Lithium Iron Manganese Phosphate Small Particles (denoted as BM 1-2a):
以Li:Mn:Fe:P的摩尔比例为1.03:0.5:0.5:1.0的比例，加入上述物料总质量的约8％的葡萄糖，按照先前所述第二规格磷酸锰铁锂的制备方法，制备出D50为4微米的磷酸锰铁锂材料；经XRD测试，其为纯相的磷酸锰铁锂材料，并结合谢乐公式计算，其一次颗粒尺寸为300nm；碳含量分析显示，其碳含量为1.7％wt。Taking the molar ratio of Li:Mn:Fe:P to be 1.03:0.5:0.5:1.0, add about 8% of the glucose of the total mass of the above-mentioned materials, and prepare according to the preparation method of the second specification lithium iron manganese phosphate previously described. The D50 is 4 microns of lithium manganese iron phosphate material; the XRD test shows that it is a pure phase lithium manganese iron phosphate material, and the primary particle size is 300nm according to the Scherrer formula calculation; the carbon content analysis shows that its carbon content is 1.7%wt.
称取BM 1-1a和BM 1-2a的磷酸锰铁锂颗粒各100g，置于球磨罐中，以50rpm的转速将物料混合均匀，得到混合均匀的产物，记为S 1。Weigh 100g each of the lithium manganese iron phosphate particles of BM 1-1a and BM 1-2a, place them in a ball mill, and mix the materials uniformly at a rotating speed of 50rpm to obtain a well-mixed product, denoted as S1.
3.比较试样3. Comparative samples
作为对比样，在BM1-1a的基础上，按照与BM1-2a同样的破碎方法，制备4微米的磷酸锰铁锂材料，并取100g该4微米磷酸锰铁锂材料与100g BM1-1a混合，置于球磨罐中，以50rpm的转速将物料混合均匀，得到混合均匀的产物，记为BM1-1b；同样，在BM1-2a的配方基础上，按照BM1-1a的方法，制备20微米的磷酸锰铁锂，并取100g与100gBM1-2a混合，置于球磨罐中，以50rpm的转速将物料混合均匀，得到混合均匀的产物，记为BM1-2b；As a comparison sample, on the basis of BM1-1a, according to the same crushing method as BM1-2a, a 4-micron lithium manganese iron phosphate material was prepared, and 100g of the 4-micron lithium manganese iron phosphate material was mixed with 100g BM1-1a, Put it in a ball mill, mix the materials evenly at a speed of 50 rpm, and obtain a uniformly mixed product, denoted as BM1-1b; similarly, on the basis of the formula of BM1-2a, according to the method of BM1-1a, prepare 20-micron phosphoric acid Lithium iron manganese, and take 100g and mix it with 100g BM1-2a, place it in a ball mill, and mix the materials evenly at a rotational speed of 50rpm to obtain a well-mixed product, denoted as BM1-2b;
BM 1-2a及b、BM 1-2a及b和S 1按照先前所述极片和扣式电池的制备方法，测试其压实密度和体积能量密度，结果汇总如表1所示。BM 1-2a and b, BM 1-2a and b and S 1 were tested for their compaction density and volumetric energy density according to the preparation method of the pole piece and coin cell previously described. The results are summarized in Table 1.
表1 实施例1的样品和参照样的压实密度和体积能量密度Table 1 The compacted density and volume energy density of the sample of Example 1 and the reference sample
Figure PCTCN2021126398-appb-000001
Figure PCTCN2021126398-appb-000001
由上面试验结果可见：采用本发明复合物制得的锂离子电池正极片具有改进的高极片压实密度和极片体积能量密度这一综合性能。对比试样BM1-1b和BM1-2b均为大颗粒磷酸锰铁锂和小颗粒磷酸锰铁锂的复合物，但是两种颗粒具有相同的锰含量，结果用这些复合物制得的锂离子电池具有相对差的极片体积能量密度。试样BM1-1a和BM1-2a为单一粒径的磷酸锰铁锂颗粒材料，这些颗粒制得的锂离子电池具有相对低的极片压实密度和极片体积能量密度。It can be seen from the above test results that the positive electrode sheet of lithium ion battery prepared by using the composite of the present invention has improved comprehensive performance of high electrode compaction density and electrode volume energy density. Comparative samples BM1-1b and BM1-2b are composites of large particles of lithium manganese iron phosphate and small particles of lithium manganese iron phosphate, but both particles have the same manganese content, resulting in lithium ion batteries made with these composites Has relatively poor pole piece volumetric energy density. The samples BM1-1a and BM1-2a are lithium manganese iron phosphate particles with a single particle size, and the lithium ion batteries prepared by these particles have relatively low pole piece compaction density and pole piece volume energy density.
实施例2Example 2
1.磷酸锰铁锂大颗粒(记为BM 2-1)的制备：1. Preparation of Lithium Iron Manganese Phosphate Large Particles (denoted as BM 2-1):
以Li:Mn:Fe:P的摩尔比例为1.04:0.3:0.7:1.0的比例，加入上述物料总质量的约6％的葡萄糖，按照先前所述第一规格磷酸锰铁锂的制备方法，制备出D50为18微米的磷酸锰铁锂材料；经XRD测试，其为纯相的磷酸锰铁锂材料，并结合谢乐公式计算，其一次颗粒尺寸为420nm；碳含量分析显示，其碳含量为1.35％wt。Taking the molar ratio of Li:Mn:Fe:P to be 1.04:0.3:0.7:1.0, add about 6% of the glucose of the total mass of the above-mentioned materials, and prepare according to the preparation method of the first specification lithium iron manganese phosphate previously described. The D50 is 18 micron lithium manganese iron phosphate material; the XRD test shows that it is a pure-phase lithium manganese iron phosphate material, and the primary particle size is 420nm according to the Scherrer formula; the carbon content analysis shows that its carbon content is 1.35%wt.
2.磷酸锰铁锂小颗粒(记为BM 2-2)的制备2. Preparation of Lithium Iron Manganese Phosphate Small Particles (denoted as BM 2-2)
以Li:Mn:Fe:P的摩尔比例为1.05:0.6:0.4:1.0的比例，加入上述物料总质量的8％的葡萄糖，按照先前所述第二规格磷酸锰铁锂的制备方法，制备出D50为3.7微米的磷酸锰铁锂材料；经XRD测试，其为纯相的磷酸锰铁锂材料，并结合谢乐公式计算，其一次颗粒尺寸为180nm；碳含量分析显示，其碳含量为1.9％wt。Taking the molar ratio of Li:Mn:Fe:P to be 1.05:0.6:0.4:1.0, adding 8% of the total mass of the above-mentioned materials, glucose, according to the previously described preparation method of the second specification lithium iron manganese phosphate, prepared. D50 is a 3.7-micron lithium manganese iron phosphate material; it is a pure-phase lithium manganese iron phosphate material by XRD test, and the primary particle size is 180 nm according to the Scherrer formula; carbon content analysis shows that its carbon content is 1.9 %wt.
按照质量比60:40的比例，各称取BM 2-1样品1200g，BM 2-2样品800g，在高混机中混合，转速300rpm，得到混合均匀的产物，记为S 2。According to the ratio of mass ratio of 60:40, each weighed 1200 g of BM 2-1 sample and 800 g of BM 2-2 sample, mixed in a high-speed mixer, and rotated at 300 rpm to obtain a uniformly mixed product, denoted as S 2 .
BM 2-2、BM 2-2和S 2按照先前所述极片和扣式电池的制备方法，测试其压实密度和体积能量密度，结果汇总如表2所示。BM 2-2, BM 2-2 and S 2 were tested for their compaction density and volumetric energy density according to the preparation method of the pole piece and button battery described previously. The results are summarized in Table 2.
表2 实施例2的样品和参照样的压实密度和体积能量密度Table 2 The compaction density and volume energy density of the sample of Example 2 and the reference sample
   BM 2-1BM 2-1 BM 2-2BM 2-2 S 2S 2
极片压实密度(g/cm 3) Pole piece compaction density (g/cm 3 ) 2.292.29 2.142.14 2.372.37
极片体积能量密度(Wh/cm 3) Pole Piece Volume Energy Density (Wh/cm 3 ) 1.201.20 1.171.17 1.271.27
实施例3Example 3
1.磷酸锰铁锂大颗粒(记为BM 3-1)的制备：1. Preparation of Lithium Iron Manganese Phosphate Large Particles (denoted as BM 3-1):
以Li:Mn:Fe:P的摩尔比例为1.03:0.4:0.6:1.0的比例，加入上述物料总质量的约 6％的葡萄糖，按照先前所述第一规格磷酸锰铁锂的制备方法，制备出D50为15微米的磷酸锰铁锂材料；经XRD测试，其为纯相的磷酸锰铁锂材料，并结合谢乐公式计算，其一次颗粒尺寸为390nm；碳含量分析显示，其碳含量为1.50％wt。Taking the molar ratio of Li:Mn:Fe:P to be 1.03:0.4:0.6:1.0, add about 6% of the glucose of the total mass of the above-mentioned materials, and prepare according to the preparation method of the first specification lithium iron manganese phosphate previously described. The D50 is 15 micron lithium manganese iron phosphate material; the XRD test shows that it is a pure phase lithium manganese iron phosphate material, and the primary particle size is 390nm according to the calculation of the Scherrer formula; the carbon content analysis shows that its carbon content is 1.50%wt.
2.磷酸锰铁锂小颗粒(记为BM 3-2)的制备2. Preparation of Lithium Iron Manganese Phosphate Small Particles (denoted as BM 3-2)
以Li:Mn:Fe:P的摩尔比例为1.05:0.7:0.3:1.0的比例，加入上述物料总质量的9％的葡萄糖，按照先前所述第二规格磷酸锰铁锂的制备方法，制备出D50为2.9微米的磷酸锰铁锂材料；经XRD测试，其为纯相的磷酸锰铁锂材料，并结合谢乐公式计算，其一次颗粒尺寸为110nm；碳含量分析显示，其碳含量为2.1％wt。Taking the molar ratio of Li:Mn:Fe:P to be 1.05:0.7:0.3:1.0, add 9% of the glucose of the total mass of the above-mentioned materials, and prepare according to the preparation method of the second specification lithium iron manganese phosphate previously described. D50 is a 2.9-micron lithium manganese iron phosphate material; it is a pure-phase lithium manganese iron phosphate material by XRD test, and the primary particle size is 110 nm according to the Scherrer formula calculation; carbon content analysis shows that its carbon content is 2.1 %wt.
按照质量比70:30的比例，各称取BM 2-1样品1400g，BM 2-2样品600g，在高混机中混合，转速300rpm，得到混合均匀的产物，记为S 3。According to the ratio of mass ratio of 70:30, each weighed 1400 g of BM 2-1 sample and 600 g of BM 2-2 sample, mixed in a high-speed mixer, and rotated at 300 rpm to obtain a uniformly mixed product, which was denoted as S 3 .
3-4BM 3-1、BM 3-2和S 3按照先前所述极片和扣式电池的制备方法，测试其压实密度和体积能量密度，结果汇总如表3所示。3-4BM 3-1, BM 3-2 and S 3 were tested for their compaction density and volumetric energy density according to the preparation method of the pole piece and button battery described previously. The results are summarized in Table 3.
表3 实施例3的样品和参照样的压实密度和体积能量密度Table 3 The compacted density and volume energy density of the sample of Example 3 and the reference sample
   BM 3-1BM 3-1 BM 3-2BM 3-2 S 3S3
极片压实密度(g/cm 3) Pole piece compaction density (g/cm 3 ) 2.282.28 1.781.78 2.422.42
极片体积能量密度(Wh/cm 3) Pole Piece Volume Energy Density (Wh/cm 3 ) 1.221.22 1.011.01 1.321.32
实施例4Example 4
1.磷酸锰铁锂大颗粒(记为BM 4-1)的制备1. Preparation of Large Lithium Iron Manganese Phosphate Particles (denoted as BM 4-1)
以Li:Mn:Fe:P的摩尔比例为1.03:0.5:0.5:1.0的比例，加入上述物料总质量的约7％的葡萄糖，按照先前所述第一规格磷酸锰铁锂的制备方法，制备出D50为12微米的磷酸锰铁锂材料；经XRD测试，其为纯相的磷酸锰铁锂材料，并结合谢乐公式计算，其一次颗粒尺寸为310nm；碳含量分析显示，其碳含量为1.8％wt。Taking the molar ratio of Li:Mn:Fe:P to be 1.03:0.5:0.5:1.0, add about 7% of the total mass of the above-mentioned materials with glucose, and prepare The D50 is 12 micron lithium manganese iron phosphate material; the XRD test shows that it is a pure phase lithium manganese iron phosphate material, and the primary particle size is 310nm according to the Scherrer formula calculation; the carbon content analysis shows that its carbon content is 1.8%wt.
2.磷酸锰铁锂小颗粒(记为BM 5-2)的制备2. Preparation of Lithium Iron Manganese Phosphate Small Particles (denoted as BM 5-2)
以Li:Mn:Fe:P的摩尔比例为1.05:0.7:0.3:1.0的比例，加入上述物料总质量的9％的葡萄糖，按照先前所述第二规格磷酸锰铁锂的制备方法，制备出D50为2.3微米的磷酸锰铁锂材料；经XRD测试，其为纯相的磷酸锰铁锂材料，并结合谢乐公式计算，其一次颗粒尺寸为80nm；碳含量分析显示，其碳含量为2.3％wt。Taking the molar ratio of Li:Mn:Fe:P to be 1.05:0.7:0.3:1.0, add 9% of the glucose of the total mass of the above-mentioned materials, and prepare according to the preparation method of the second specification lithium iron manganese phosphate previously described. D50 is a 2.3-micron lithium manganese iron phosphate material; after XRD test, it is a pure phase lithium manganese iron phosphate material, and the primary particle size is 80nm according to Scherrer formula calculation; carbon content analysis shows that its carbon content is 2.3 %wt.
按照质量比70:30的比例，各称取BM 4-1样品1400g，BM 4-2样品600g，在 高混机中混合，转速300rpm，得到混合均匀的产物，记为S 4。According to the ratio of mass ratio 70:30, each take BM 4-1 sample 1400g, BM 4-2 sample 600g, mix in high mixer, rotating speed 300rpm, obtain the product that mixes homogeneously, denoted as S 4.
BM 4-1、BM 4-2和S 4按照先前所述极片和扣式电池的制备方法，测试其压实密度和体积能量密度，结果汇总如表4所示。BM 4-1, BM 4-2 and S 4 were tested for their compaction density and volumetric energy density according to the preparation method of the pole piece and button battery described previously. The results are summarized in Table 4.
图1，图2和图3分别为实施例4的S 4样品的SEM图，XRD图和充放电曲线图。Figure 1, Figure 2 and Figure 3 are the SEM image, XRD image and charge-discharge curve diagram of the S4 sample of Example 4, respectively.
表4 实施例4的样品和参照样的压实密度和体积能量密度Table 4 The compacted density and volume energy density of the sample of Example 4 and the reference sample
   BM 4-1BM 4-1 BM 4-2BM 4-2 S 4S 4
极片压实密度(g/cm 3) Pole piece compaction density (g/cm 3 ) 2.282.28 1.781.78 2.422.42
极片体积能量密度(Wh/cm 3) Pole Piece Volume Energy Density (Wh/cm 3 ) 1.201.20 1.011.01 1.321.32
实施例5Example 5
1.磷酸锰铁锂大颗粒(记为BM 5-1)的制备1. Preparation of large lithium iron manganese phosphate particles (denoted as BM 5-1)
以Li:Mn:Fe:P的摩尔比例为1.04:0.6:0.4:1.0的比例，加入上述物料总质量的约9％的葡萄糖，按照先前所述第一规格磷酸锰铁锂的制备方法，制备出D50为10微米的磷酸锰铁锂材料；经XRD测试，其为纯相的磷酸锰铁锂材料，并结合谢乐公式计算，其一次颗粒尺寸为260nm；碳含量分析显示，其碳含量为2.1％wt。Taking the molar ratio of Li:Mn:Fe:P to be 1.04:0.6:0.4:1.0, add about 9% of the glucose of the total mass of the above-mentioned materials, and prepare according to the preparation method of the first specification lithium iron manganese phosphate previously described. The D50 is 10 micron lithium manganese iron phosphate material; the XRD test shows that it is a pure-phase lithium manganese iron phosphate material, and the primary particle size is 260nm according to the Scherrer formula calculation; the carbon content analysis shows that its carbon content is 2.1%wt.
2.磷酸锰铁锂小颗粒(记为BM 5-2)的制备2. Preparation of Lithium Iron Manganese Phosphate Small Particles (denoted as BM 5-2)
以Li:Mn:Fe:P的摩尔比例为1.05:0.75:0.25:1.0的比例，加入上述物料总质量的11％的葡萄糖，按照先前所述第二规格磷酸锰铁锂的制备方法，制备出D50为1.7微米的磷酸锰铁锂材料；经XRD测试，其为纯相的磷酸锰铁锂材料，并结合谢乐公式计算，其一次颗粒尺寸为60nm；碳含量分析显示，其碳含量为2.9％wt。Taking the molar ratio of Li:Mn:Fe:P to be 1.05:0.75:0.25:1.0, add 11% of the glucose of the total mass of the above-mentioned materials, and prepare according to the preparation method of the second specification lithium iron manganese phosphate previously described. D50 is a 1.7-micron lithium manganese iron phosphate material; it is a pure-phase lithium manganese iron phosphate material by XRD test, and the primary particle size is 60nm according to the Scherrer formula calculation; carbon content analysis shows that its carbon content is 2.9 %wt.
按照质量比75:25的比例，各称取BM 5-1样品1500g，BM 5-2样品500g，在高混机中混合，转速300rpm，得到混合均匀的产物，记为S 5。According to the ratio of mass ratio of 75:25, 1500 g of BM 5-1 sample and 500 g of BM 5-2 sample were weighed, mixed in a high-speed mixer, and the rotating speed was 300 rpm to obtain a uniformly mixed product, denoted as S 5.
BM 5-1、BM 5-2和S 5按照先前所述极片和扣式电池的制备方法，测试其压实密度和体积能量密度，结果汇总如表5所示。BM 5-1, BM 5-2 and S 5 were tested for their compaction density and volumetric energy density according to the preparation method of the pole piece and button battery described previously. The results are summarized in Table 5.
表5 实施例5的样品和参照样的压实密度和体积能量密度Table 5 The compacted density and volume energy density of the sample of Example 5 and the reference sample
   BM 5-1BM 5-1 BM 5-2BM 5-2 S 5S 5
极片压实密度(g/cm 3) Pole piece compaction density (g/cm 3 ) 2.242.24 1.771.77 2.392.39
极片体积能量密度(Wh/cm 3) Pole Piece Volume Energy Density (Wh/cm 3 ) 1.251.25 1.041.04 1.341.34
实施例6Example 6
1.磷酸锰铁锂大颗粒(记为BM 6-1)的制备1. Preparation of Large Lithium Iron Manganese Phosphate Particles (denoted as BM 6-1)
以Li:Mn:Fe:P的摩尔比例为1.05:0.7:0.3:1.0的比例，加入上述物料总质量的约9％的葡萄糖，按照先前所述第一规格磷酸锰铁锂的制备方法，制备出D50为8微米的磷酸锰铁锂材料；经XRD测试，其为纯相的磷酸锰铁锂材料，并结合谢乐公式计算，其一次颗粒尺寸为260nm；碳含量分析显示，其碳含量为2.3％wt。Taking the molar ratio of Li:Mn:Fe:P to be 1.05:0.7:0.3:1.0, add about 9% of the glucose of the total mass of the above-mentioned materials, and prepare according to the preparation method of the first specification lithium iron manganese phosphate previously described. The D50 is 8 microns lithium manganese iron phosphate material; the XRD test shows that it is a pure-phase lithium manganese iron phosphate material, and the primary particle size is 260 nm according to the Scherrer formula; the carbon content analysis shows that its carbon content is 2.3%wt.
2.磷酸锰铁锂小颗粒(记为BM 6-2)的制备2. Preparation of small lithium iron manganese phosphate particles (denoted as BM 6-2)
以Li:Mn:Fe:P的摩尔比例为1.05:0.8:0.2:1.0的比例，加入上述物料总质量的11％的葡萄糖，按照先前所述第二规格磷酸锰铁锂的制备方法，制备出D50为1.2微米的磷酸锰铁锂材料；经XRD测试，其为纯相的磷酸锰铁锂材料，并结合谢乐公式计算，其一次颗粒尺寸为50nm；碳含量分析显示，其碳含量为2.8％wt。Taking the molar ratio of Li:Mn:Fe:P to be 1.05:0.8:0.2:1.0, add 11% of the glucose of the total mass of the above-mentioned materials, and prepare according to the preparation method of the second specification lithium iron manganese phosphate previously described. D50 is a 1.2-micron lithium manganese iron phosphate material; the XRD test shows that it is a pure phase lithium manganese iron phosphate material, and the primary particle size is 50nm according to the Scherrer formula; the carbon content analysis shows that its carbon content is 2.8 %wt.
按照质量比80:20的比例，各称取BM 6-1样品1600g，BM 6-2样品400g，在高混机中混合，转速300rpm，得到混合均匀的产物，记为S 6。According to the ratio of mass ratio of 80:20, each weighed 1600 g of BM 6-1 sample and 400 g of BM 6-2 sample, mixed in a high-speed mixer, and rotated at 300 rpm to obtain a well-mixed product, denoted as S 6.
BM 6-1、BM 6-2和S 6按照先前所述极片和扣式电池的制备方法，测试其压实密度和体积能量密度，结果汇总如表6所示。BM 6-1, BM 6-2 and S 6 were tested for their compaction density and volumetric energy density according to the preparation method of the pole piece and button battery described previously. The results are summarized in Table 6.
表6 实施例6的样品和参照样的压实密度和体积能量密度Table 6 The compacted density and volume energy density of the sample of Example 6 and the reference sample
   BM 6-1BM 6-1 BM 6-2BM 6-2 S 6S 6
极片压实密度(g/cm 3) Pole piece compaction density (g/cm 3 ) 2.12.1 1.71.7 2.272.27
极片体积能量密度(Wh/cm 3) Pole Piece Volume Energy Density (Wh/cm 3 ) 1.201.20 1.011.01 1.301.30
实施例7Example 7
1.磷酸锰铁锂大颗粒(记为BM 7-1)的制备1. Preparation of large lithium iron manganese phosphate particles (denoted as BM 7-1)
以Li:Mn:Fe:P的摩尔比例为1.05:0.8:0.2:1.0的比例，加入上述物料总质量的约10％的葡萄糖，按照先前所述第一规格磷酸锰铁锂的制备方法，制备出D50为5微米的磷酸锰铁锂材料；经XRD测试，其为纯相的磷酸锰铁锂材料，并结合谢乐公式计算，其一次颗粒尺寸为80nm；碳含量分析显示，其碳含量为2.8％wt。Taking the molar ratio of Li:Mn:Fe:P to be 1.05:0.8:0.2:1.0, adding about 10% of the total mass of the above-mentioned materials, glucose, according to the previously described preparation method of the first specification lithium iron manganese phosphate, to prepare The D50 is 5 microns lithium manganese iron phosphate material; the XRD test shows that it is a pure phase lithium manganese iron phosphate material, and the primary particle size is 80 nm according to the calculation of Scherrer formula; the carbon content analysis shows that its carbon content is 2.8%wt.
2.磷酸锰铁锂小颗粒(记为BM 7-2)的制备2. Preparation of Lithium Iron Manganese Phosphate Small Particles (denoted as BM 7-2)
以Li:Mn:Fe:P的摩尔比例为1.05:0.85:0.15:1.0的比例，加入上述物料总质量的 11％的葡萄糖，按照先前所述第二规格磷酸锰铁锂的制备方法，制备出D50为0.8微米的磷酸锰铁锂材料；经XRD测试，其为纯相的磷酸锰铁锂材料，并结合谢乐公式计算，其一次颗粒尺寸为39nm；碳含量分析显示，其碳含量为2.9％wt。Taking the molar ratio of Li:Mn:Fe:P to be 1.05:0.85:0.15:1.0, add 11% of the total mass of the above-mentioned material glucose, according to the previously described preparation method of the second specification lithium iron manganese phosphate, to prepare D50 is a 0.8-micron lithium manganese iron phosphate material; it is a pure-phase lithium manganese iron phosphate material by XRD test, and the primary particle size is 39nm according to the Scherrer formula; the carbon content analysis shows that its carbon content is 2.9 %wt.
按照质量比90:10的比例，各称取BM 7-1样品1800g，BM 7-2样品200g，在高混机中混合，转速300rpm，得到混合均匀的产物，记为S 7。According to the ratio of mass ratio of 90:10, 1800 g of BM 7-1 sample and 200 g of BM 7-2 sample were weighed, and mixed in a high-speed mixer at a rotational speed of 300 rpm to obtain a uniformly mixed product, denoted as S7.
BM 7-1、BM 7-2和S 7按照先前所述极片和扣式电池的制备方法，测试其压实密度和体积能量密度，结果汇总如表表7所示。BM 7-1, BM 7-2 and S 7 were tested for their compaction density and volumetric energy density according to the preparation method of the pole piece and button battery described previously. The results are summarized in Table 7.
表7 实施例7的样品和参照样的压实密度和体积能量密度Table 7 The compacted density and volume energy density of the sample of Example 7 and the reference sample
   BM 7-1BM 7-1 BM 7-2BM 7-2 S 7S7
极片压实密度(g/cm 3) Pole piece compaction density (g/cm 3 ) 1.91.9 1.671.67 2.052.05
极片体积能量密度(Wh/cm 3) Pole Piece Volume Energy Density (Wh/cm 3 ) 1.131.13 1.011.01 1.221.22

Claims (10)

  1. 一种磷酸锰铁锂复合材料，以重量计它包括：A lithium iron manganese phosphate composite material, comprising by weight:
    a)50-90％大颗粒磷酸锰铁锂，其一次粒径为80-500nm，二次粒径为5-20μm，按所述磷酸锰铁锂材料中除锂以外的金属元素的总摩尔数计，磷酸锰铁锂材料中锰元素的含量为20-80％；a) 50-90% large particle lithium iron manganese phosphate, the primary particle size is 80-500nm, and the secondary particle size is 5-20μm, according to the total moles of metal elements other than lithium in the lithium iron manganese phosphate material In total, the content of manganese in the lithium iron manganese phosphate material is 20-80%;
    b)10-50％小颗粒磷酸锰铁锂，其一次粒径为30-200nm，二次粒径为0.5-4μm，按所述磷酸锰铁锂材料中除锂以外的金属元素的总摩尔数计，磷酸锰铁锂材料中锰元素的含量为50-90％；b) 10-50% small particle lithium iron manganese phosphate, the primary particle size is 30-200nm, and the secondary particle size is 0.5-4 μm, according to the total moles of metal elements other than lithium in the lithium iron manganese phosphate material In total, the content of manganese in the lithium iron manganese phosphate material is 50-90%;
    所述大颗粒磷酸锰铁锂的锰含量要低于所述小颗粒磷酸锰铁锂的锰含量。The manganese content of the large particle lithium iron manganese phosphate is lower than the manganese content of the small particle lithium manganese iron phosphate.
  2. 如权利要求1所述的磷酸锰铁锂复合材料，其特征在于所述大颗粒磷酸锰铁锂的一次粒径为100-400nm；二次粒径为7-15μm。The lithium iron manganese phosphate composite material according to claim 1, wherein the primary particle size of the large particle lithium manganese iron phosphate is 100-400 nm; the secondary particle size is 7-15 μm.
  3. 如权利要求1所述的磷酸锰铁锂复合材料，其特征在于，按所述磷酸锰铁锂材料中除锂以外的金属元素的总摩尔数计，所述大颗粒磷酸锰铁锂中锰元素的含量为40-75％，更优为55-65％。The lithium iron manganese phosphate composite material according to claim 1, wherein, according to the total number of moles of metal elements other than lithium in the lithium iron manganese phosphate material, the manganese element in the large particle lithium iron manganese phosphate The content is 40-75%, more preferably 55-65%.
  4. 如权利要求1所述的磷酸锰铁锂复合材料，其特征在于，所述小颗粒磷酸锰铁锂的一次粒径为35-150nm，更好为40-100nm，优选45-80nm；二次粒径为0.8-3.5μm。The lithium manganese iron phosphate composite material according to claim 1, wherein the primary particle size of the small particles of lithium manganese iron phosphate is 35-150 nm, more preferably 40-100 nm, preferably 45-80 nm; The diameter is 0.8-3.5μm.
  5. 如权利要求1所述的磷酸锰铁锂复合材料，其特征在于，按所述磷酸锰铁锂材料中除锂以外的金属元素的总摩尔数计，所述小颗粒磷酸锰铁锂中锰元素的含量为为60-88％。The lithium iron manganese phosphate composite material according to claim 1, wherein, according to the total number of moles of metal elements other than lithium in the lithium iron manganese phosphate material, the manganese element in the small particle lithium iron manganese phosphate The content is 60-88%.
  6. 如权利要求1-5中任一项所述的磷酸锰铁锂复合材料，其特征在于，按所述磷酸锰铁锂材料中除锂以外的金属元素的总摩尔数计，所述小颗粒磷酸锰铁锂的锰含量比大颗粒磷酸锰铁锂的锰含量高至少0.1％，较好至少高0.3％，更好至少高0.5％，宜至少高0.8％，最好至少高1.0％，优选至少高1.5％。The lithium iron manganese phosphate composite material according to any one of claims 1 to 5, wherein the small particle phosphoric acid is calculated by the total moles of metal elements other than lithium in the lithium iron manganese phosphate material. The manganese content of the lithium iron manganese is at least 0.1% higher than the manganese content of the large particle lithium iron manganese phosphate, preferably at least 0.3% higher, more preferably at least 0.5% higher, preferably at least 0.8% higher, preferably at least 1.0% higher, preferably at least 1.5% higher.
  7. 如权利要求1-5中任一项所述的磷酸锰铁锂复合材料，其特征在于，以重量计，所述磷酸锰铁锂大颗粒的含量为60-88％，更好65-85％，优选70-80％；所述小颗粒磷酸锰铁锂的含量为12-40％，更好15-35％，优选20-30％。The lithium iron manganese phosphate composite material according to any one of claims 1 to 5, wherein the content of the large particles of lithium iron manganese phosphate is 60-88%, more preferably 65-85% by weight , preferably 70-80%; the content of the small particles of lithium iron manganese phosphate is 12-40%, more preferably 15-35%, preferably 20-30%.
  8. 如权利要求1-7中任一项所述的磷酸锰铁锂复合材料的制备方法，它包括如下步骤：The preparation method of the lithium iron manganese phosphate composite material according to any one of claims 1-7, it comprises the steps:
    a)按复合材料的总重量计，提供50-90％大颗粒磷酸锰铁锂，其一次粒径为80-500nm，二次粒径为5-20μm，按所述磷酸锰铁锂材料中除锂以外的金属元素的总摩尔数计，磷酸锰铁锂材料中锰元素的含量为20-80％；a) According to the total weight of the composite material, provide 50-90% large particle lithium iron manganese phosphate, whose primary particle size is 80-500nm, and the secondary particle size is 5-20μm, according to the removal of the lithium iron manganese phosphate material. In terms of the total moles of metal elements other than lithium, the content of manganese element in the lithium iron manganese phosphate material is 20-80%;
    b)提供10-50％小颗粒磷酸锰铁锂，其一次粒径为30-200nm，二次粒径为0.5-4μm，按所述磷酸锰铁锂材料中除锂以外的金属元素的总摩尔数计，磷酸锰铁锂材料中锰元素的含量为50-90％；b) Provide 10-50% small particle lithium iron manganese phosphate with a primary particle size of 30-200 nm and a secondary particle size of 0.5-4 μm, according to the total moles of metal elements other than lithium in the lithium iron manganese phosphate material In terms of numbers, the content of manganese in the lithium iron manganese phosphate material is 50-90%;
    其中，所述大颗粒磷酸锰铁锂的锰含量要低于所述小颗粒磷酸锰铁锂的锰含量；Wherein, the manganese content of the large particle lithium manganese iron phosphate is lower than the manganese content of the small particle lithium manganese iron phosphate;
    c)混合所述大颗粒磷酸锰铁锂和所述小颗粒磷酸锰铁锂。c) Mixing the large particles of lithium iron manganese phosphate and the small particles of lithium iron manganese phosphate.
  9. 如权利要求8所述的方法，其特征在于，按所述磷酸锰铁锂材料中除锂以外的金属元素的总摩尔数计，所述小颗粒磷酸锰铁锂的锰含量比大颗粒磷酸锰铁锂的锰含量高至少0.1％，较好至少高0.3％，更好至少高0.5％，宜至少高0.8％，最好至少高1.0％，优选至少高1.5％。The method according to claim 8, characterized in that, in terms of the total moles of metal elements other than lithium in the lithium iron manganese phosphate material, the manganese content of the small particles of lithium iron manganese phosphate is higher than that of the large particles of manganese iron phosphate. The manganese content of the iron lithium is at least 0.1% higher, preferably at least 0.3% higher, more preferably at least 0.5% higher, preferably at least 0.8% higher, preferably at least 1.0% higher, preferably at least 1.5% higher.
  10. 用权利要求1-7中任一项所述的磷酸锰铁锂复合材料制得的锂离子电池正极。A lithium ion battery positive electrode prepared with the lithium manganese iron phosphate composite material according to any one of claims 1-7.
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