CN114583159B - Low-temperature lithium iron phosphate positive electrode material, preparation method and application thereof - Google Patents
Low-temperature lithium iron phosphate positive electrode material, preparation method and application thereof Download PDFInfo
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000007774 positive electrode material Substances 0.000 title claims description 18
- 238000005245 sintering Methods 0.000 claims abstract description 39
- 239000006185 dispersion Substances 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 229910007857 Li-Al Inorganic materials 0.000 claims abstract description 20
- 229910008447 Li—Al Inorganic materials 0.000 claims abstract description 20
- 239000010405 anode material Substances 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 15
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 13
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 13
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 13
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 12
- 150000001720 carbohydrates Chemical class 0.000 claims abstract description 11
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 11
- 238000001694 spray drying Methods 0.000 claims abstract description 10
- 239000011229 interlayer Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000001413 cellular effect Effects 0.000 claims abstract description 8
- 238000005507 spraying Methods 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 230000001681 protective effect Effects 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 16
- 229910001416 lithium ion Inorganic materials 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 11
- 239000008103 glucose Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 8
- 238000000713 high-energy ball milling Methods 0.000 claims description 7
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 150000004692 metal hydroxides Chemical class 0.000 claims description 5
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 3
- 229930091371 Fructose Natural products 0.000 claims description 3
- 239000005715 Fructose Substances 0.000 claims description 3
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 3
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 239000011149 active material Substances 0.000 claims description 3
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 3
- 229930182830 galactose Natural products 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 238000003801 milling Methods 0.000 claims description 3
- 239000004576 sand Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 description 17
- 239000003792 electrolyte Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000005056 compaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 150000004679 hydroxides Chemical class 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 102220043159 rs587780996 Human genes 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 235000014633 carbohydrates Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a low-temperature lithium iron phosphate anode material, a preparation method and application thereof, wherein the preparation method mainly comprises the following steps: mixing cellular ferric phosphate, a lithium source and a saccharide substance with water, and sanding to obtain a dispersion liquid; spray drying the dispersion liquid to obtain a precursor; and sintering the precursor in a protective atmosphere, and simultaneously, taking part in sintering the layered Li-Al double-metal hydroxide in a dry powder spraying mode to prepare the low-temperature lithium iron phosphate anode material. The invention takes honeycomb ferric phosphate as a raw material, and forms a special interlayer structure in the preparation process of the lithium iron phosphate anode material by utilizing layered double hydroxide (Li-Al LDH), thereby greatly improving the low-temperature performance of the lithium iron phosphate anode material.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, and particularly relates to a preparation method of a low-temperature type lithium iron phosphate anode material, a low-temperature type lithium iron phosphate anode material prepared by the preparation method and application of the low-temperature type lithium iron phosphate anode material in a lithium ion battery.
Background
LiFePO 4 The electrode material has the advantages of high specific capacity, stable working voltage, low cost, environmental friendliness and the like, is regarded as an ideal lithium ion battery anode material, and is one of main anode materials of the current electric automobile.
However, at low temperature LiFePO 4 The battery performance is significantly reduced, limiting its use in winter and alpine regions. Many researchers have conducted mechanical studies on the phenomenon of accelerated degradation of performance of lithium ion batteries at low temperatures, and believed to be primarily the deposition of active lithium and its catalytically grown solid electrolyte interface, resulting in a decrease in ionic conductivity and a decrease in electron transfer rate in the electrolyte, which results in a decrease in capacity and power of lithium ion batteries, and sometimes even in battery performance failures. The low-temperature working environment of the lithium ion battery mainly occurs in winter and at high latitude and high altitudeThe low temperature environment therein affects the performance and lifetime of lithium ion batteries and even causes extremely serious safety problems. And the lithium intercalation speed of graphite is reduced under the influence of low temperature, lithium dendrite is easily formed by precipitating metal lithium on the surface of the negative electrode, and the separator is punctured, so that the internal short circuit of the battery is caused. Therefore, the method for improving the low-temperature performance of the lithium ion battery has important significance for popularization and use of the electric automobile in high and cold areas.
The existing main methods for improving the low-temperature performance of the lithium iron phosphate battery comprise material nanocrystallization, metal doping, carbon coating and the like, the effect is not obvious, the material structure is easy to collapse in the use process, and the recycling service life of the lithium iron phosphate battery is reduced.
Disclosure of Invention
In view of the foregoing, it is desirable to provide a method for preparing a low-temperature type lithium iron phosphate positive electrode material, in which a layered double hydroxide (Li-Al LDH) is used as a raw material to form a special interlayer structure during the preparation of the lithium iron phosphate positive electrode material, thereby greatly improving the low-temperature performance of the lithium iron phosphate positive electrode material.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention firstly provides a preparation method of a low-temperature lithium iron phosphate positive electrode material, which comprises the following steps:
mixing cellular ferric phosphate, a lithium source and a saccharide substance with water, and sanding to obtain a dispersion liquid;
spray drying the dispersion liquid to obtain a precursor;
and sintering the precursor in a protective atmosphere, and simultaneously, taking part in sintering the layered Li-Al double-metal hydroxide in a dry powder spraying mode to prepare the low-temperature lithium iron phosphate anode material.
Further, the ratio of the honeycomb ferric phosphate to the lithium source is 1 according to the stoichiometric ratio of Fe to Li: (1-1.1), wherein the lithium source is selected from one or a mixture of two of lithium hydroxide and lithium carbonate.
Further, the sand milling adopts a high-energy ball milling mode, and the ball milling time is 1-4h.
Further, the particle size D50 of the dispersion is in the range of 200-300nm.
Further, the saccharide is selected from one or two of glucose, fructose, galactose, sucrose, maltose and starch; the adding amount of the saccharide is controlled to be 1.0-1.3wt% of the carbon content after sintering the lithium iron phosphate.
Further, the protective atmosphere is selected from one or more than two of high-purity nitrogen, high-purity helium and high-purity argon.
Further, the interlayer spacing of the layered Li-Al duplex metal hydroxide is 0.1-1.5nm.
Further, the sintering adopts step-by-step sintering, and the step-by-step sintering specifically comprises the following steps: presintering at 300-450 deg.C, and sintering at 700-800 deg.C.
The invention also provides a low-temperature lithium iron phosphate positive electrode material which is prepared by adopting the preparation method according to any one of the above.
The invention further provides a lithium ion battery, which comprises a positive electrode, wherein the active material of the positive electrode contains the low-temperature type lithium iron phosphate positive electrode material.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, cellular ferric phosphate is used as a raw material, a small amount of Li-Al LDH is used as a material macrostructure template, the steps of mixing, sanding, drying and the like are carried out, the purposeful growth of the lithium iron phosphate material in the preparation process is promoted, then the target interlayer structure is formed through high-temperature sintering, after the lithium iron phosphate material with the structure is manufactured into a battery, a micro-region pillared structure is formed with lithium salt in electrolyte, and the structure can regulate and control the active sites on the material to generate charge transfer and mass transfer while stabilizing a material system, so that the lithium ions can shuttle at low temperature, and the low-temperature performance of the lithium iron phosphate anode material can be greatly improved.
Detailed Description
The following detailed description of embodiments of the invention is exemplary and is provided merely to illustrate the invention and is not to be construed as limiting the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The invention provides a preparation method of a low-temperature lithium iron phosphate positive electrode material, which mainly comprises the following steps:
preparation of the precursor
Specifically, cellular ferric phosphate FePO 4 Mixing a lithium source, a sugar substance and deionized water, and sanding to obtain a dispersion liquid; and then spray drying the dispersion liquid to obtain the precursor. The honeycomb ferric phosphate can provide carbohydrate as a carbon source and the growth site of the subsequent layered Li-Al double metal hydroxide, so that the structure of the interlayer structure of the lithium iron phosphate anode material is facilitated. It will be appreciated that the choice of lithium source and carbohydrate is not particularly limited and may be employed as raw materials conventionally used in the art for the preparation of lithium iron phosphate, and in one or more embodiments of the present invention, the lithium source is selected from one or a mixture of two of lithium hydroxide, lithium carbonate, and the carbohydrate is selected from one or a mixture of two of glucose, fructose, galactose, sucrose, maltose, and starch.
Further, the proportion of each component in the precursor can be selected according to actual conditions, and according to the embodiment of the invention, the proportion of the cellular ferric phosphate to the lithium source is 1 according to the stoichiometric ratio of Fe to Li: (1-1.1) and controlling the adding amount of the saccharide substance to be 1.0-1.3wt% of the carbon content after sintering the lithium iron phosphate.
Further, in the present invention, the granularity of the raw materials is controlled by sand milling to improve the reactivity, and in the embodiment of the present invention, a high-energy ball milling method is adopted, the ball milling time is 1-4 hours, and it is understood that the ball milling time is not particularly limited, and the adjustment can be performed according to the actual situation, so long as the dispersion liquid reaches the target granularity.
Furthermore, the method adopts a spray drying mode to uniformly embed the sugar substances into the honeycomb FePO 4 Inside, the positioning of later Li-Al LDH is facilitated, and in particular, the uniform embedding of saccharide substances can be regulated and controlled through spray drying.
Preparation of lithium iron phosphate cathode material
The preparation method comprises the steps of carrying out sintering on the obtained precursor in a protective atmosphere, and simultaneously, taking part in sintering the layered Li-Al double-metal hydroxide in a dry powder spraying mode, so that the layered Li-Al double-metal hydroxide is uniformly sprayed into ferric phosphate, and preparing the low-temperature lithium iron phosphate anode material. As the high purity inert gas or nitrogen gas having a purity of more than 99.999% used herein, examples which may be mentioned include, but are not limited to, one or a mixture of two or more of high purity nitrogen gas, high purity argon gas, high purity helium gas; further, the layered double hydroxides (layered double hydroxides, LDHs) are metal hydroxides composed of two or more metal elements, the structure is formed by overlapping a main laminate, anions and water molecules among layers, the layered Li-Al double hydroxides Li-Al LDH are adopted as a material macrostructure template, so that a special interlayer structure is formed in the process of preparing the lithium iron phosphate material, after the lithium iron phosphate material with the structure is prepared into a battery, a micro-region pillared structure is formed with part of lithium salt in the electrolyte in the process of charging and discharging along with infiltration of the electrolyte, so that the shuttle movement of lithium ions at low temperature is facilitated, the low-temperature performance of the lithium iron phosphate positive electrode material can be greatly improved, and preferably, the interlayer spacing of the layered Li-Al double hydroxides is 0.1-1.5nm.
Further, in the embodiment of the invention, the distributed sintering is adopted, specifically, the sintering is firstly performed at 300-450 ℃ for 4-6 hours, and then the sintering is performed at 700-800 ℃ for 5-10 hours. Preferably, in the embodiment of the invention, the rotary kiln is adopted for sintering, and the rotary kiln is matched with a dry powder spraying device.
According to the invention, based on cellular ferric phosphate, by introducing double metal hydroxides to participate in sintering, a micro-region pillared structure is formed with lithium salt in electrolyte in the construction process of a lithium iron phosphate material system, and the structure can regulate and control active sites on a material to perform charge transfer and mass transfer while stabilizing the material system, so that the shuttle movement of lithium ions at low temperature is facilitated, and the low-temperature performance of a lithium iron phosphate anode material and the compaction density of the material can be greatly improved.
In a second aspect, the invention provides a low-temperature lithium iron phosphate positive electrode material, which is prepared by the preparation method according to any one of the first aspects of the invention. The low-temperature lithium iron phosphate positive electrode material has a special interlayer structure, so that after the lithium ion battery is manufactured, a micro-region column support structure is formed with part of lithium salt in electrolyte in the charging and discharging process along with the infiltration of the electrolyte, and the low-temperature performance of the lithium iron phosphate positive electrode material is greatly improved.
The third aspect of the invention provides a lithium ion battery, which comprises a positive electrode, wherein an active material of the positive electrode contains the low-temperature lithium iron phosphate positive electrode material according to the second aspect of the invention, the lithium ion battery has a normal temperature of 25 ℃, a 1C charge-discharge capacity retention rate of more than 99%, a low temperature of-10 ℃, and a 1C charge-discharge capacity retention rate of more than 80%, and can completely meet the use requirement in a low-temperature environment.
The present invention will be illustrated by the following examples, which are given for illustrative purposes only and are not intended to limit the scope of the present invention in any way, and unless otherwise specified, the conditions or procedures not specifically described are conventional and the reagents and materials employed are commercially available.
Example 1
S1, according to stoichiometric ratio Fe: li=1:1.05 honeycomb FePO was weighed out 4 Adding glucose (the addition amount is controlled to be 1.2 percent of carbon content after sintering of lithium iron phosphate) into lithium carbonate, sequentially adding the lithium iron phosphate and the lithium iron phosphate into deionized water to disperse for 2.5 hours, performing high-energy ball milling for 3 hours to obtain a dispersion liquid, and performing ball milling to obtain a particle size D50=250 nm;
s2, spray drying the dispersion liquid to uniformly embed glucose into the honeycomb FePO 4 Obtaining a precursor;
s3, sintering the precursor in a rotary kiln under the protection of high-purity nitrogen, wherein the precursor is sintered for 5 hours at 400 ℃ and 8 hours at 750 ℃; meanwhile, adding Li-Al LDH into a rotary kiln through a dry powder spraying device according to a mass ratio of 1:100 to participate in sintering, and preparing and obtaining the low-temperature lithium iron phosphate anode material after natural cooling, wherein the powder compaction can reach 2.42g/cc.
Example 2
S1, according to stoichiometric ratio Fe: li=1:1 honeycomb FePO was weighed out 4 Adding glucose (the addition amount is controlled to be 1.0 percent of carbon content after sintering of lithium iron phosphate) into lithium carbonate, sequentially adding the lithium iron phosphate and the lithium iron phosphate into deionized water for dispersion for 2 hours, performing high-energy ball milling for 1 hour to obtain dispersion liquid, and performing ball milling to obtain the particle size D50=200 nm;
s2, spray drying the dispersion liquid to uniformly embed glucose into the honeycomb FePO 4 Obtaining a precursor;
s3, sintering the precursor in a rotary kiln under the protection of high-purity nitrogen, wherein the precursor is sintered for 4 hours at 300 ℃ and sintered for 5 hours at 700 ℃; meanwhile, adding Li-Al LDH into a rotary kiln through a dry powder spraying device according to the mass ratio of 0.2:100 to participate in sintering, and preparing and obtaining the low-temperature lithium iron phosphate anode material after natural cooling, wherein the powder compaction can reach 2.4g/cc.
Example 3
S1, according to stoichiometric ratio Fe: li=1:1.1 honeycomb FePO was weighed out 4 Adding glucose (the addition amount is controlled to be 1.3 percent of carbon content after sintering of lithium iron phosphate) into lithium carbonate, sequentially adding the lithium iron phosphate and the lithium iron phosphate into deionized water for dispersion for 3 hours, performing high-energy ball milling for 4 hours to obtain a dispersion liquid, and performing ball milling to obtain a particle size D50=300 nm;
s2, spray drying the dispersion liquid to uniformly embed glucose into the honeycomb FePO 4 Obtaining a precursor;
s3, sintering the precursor in a rotary kiln under the protection of high-purity nitrogen, wherein the sintering is carried out for 6 hours at 450 ℃ and 10 hours at 800 ℃; meanwhile, adding Li-Al LDH into a rotary kiln through a dry powder spraying device according to the mass ratio of 1.5:100 to participate in sintering, and preparing and obtaining the low-temperature lithium iron phosphate anode material after natural cooling, wherein the powder compaction can reach 2.39g/cc.
Comparative example 1
S1, according to stoichiometric ratio Fe: li=1:1.05 honeycomb FePO was weighed out 4 Adding glucose (the addition amount is controlled to be 1.1 percent of carbon content after sintering of lithium iron phosphate) into lithium carbonate, sequentially adding the lithium iron phosphate and the lithium iron phosphate into deionized water to disperse for 2.5 hours, performing high-energy ball milling for 3 hours to obtain a dispersion liquid, and performing ball milling to obtain a particle size D50=250 nm;
s2, spray drying the dispersion liquid to uniformly embed glucose into the honeycomb FePO 4 Obtaining a precursor;
s3, sintering the precursor in a rotary kiln under the protection of high-purity nitrogen, sintering for 5h at 400 ℃ and sintering for 8h at 750 ℃, naturally cooling to prepare the lithium iron phosphate anode material, and compacting the powder to 2.3g/cc.
Test case
The lithium iron phosphate positive electrode materials prepared in examples 1 to 3 and comparative example 1 were fabricated into a single sheet soft pack, and 1C charge and discharge were performed at normal temperature (25 ℃ C.) and low temperature (-10 ℃ C.) respectively, and the charge and discharge capacity retention rate values were measured, and the results are shown in Table 1.
Table 1 single chip soft pack performance test
As can be seen from the test results in table 1, examples 1, 2 and 3 all have a capacity retention rate of 80% or more at low temperature (-10 ℃), and especially example 1 shows a capacity retention rate of 88.6% at low temperature, whereas the lithium iron phosphate material prepared by the conventional method of comparative example 1 has a capacity retention rate of only 30.5% at low temperature, indicating that the lithium iron phosphate material obtained by the preparation method of the present invention has excellent low temperature performance.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (7)
1. The preparation method of the low-temperature lithium iron phosphate positive electrode material is characterized by comprising the following steps of:
mixing cellular ferric phosphate, a lithium source and a saccharide substance with water, and sanding to obtain a dispersion liquid;
spray drying the dispersion liquid to obtain a precursor;
sintering the precursor in a protective atmosphere, and simultaneously, participating in sintering of layered Li-Al double-metal hydroxide in a dry powder spraying mode, so that the layered Li-Al double-metal hydroxide is uniformly sprayed into ferric phosphate to prepare a low-temperature lithium iron phosphate anode material;
wherein the saccharide is selected from one or two of glucose, fructose, galactose, sucrose, maltose and starch; the adding amount of the sugar substances is controlled to be 1.0-1.3wt% of the carbon content after sintering the lithium iron phosphate; the mass ratio of the layered Li-Al bimetallic hydroxide to the precursor is (0.2-1.5): 100; the sintering adopts step sintering, and the step sintering specifically comprises the following steps: presintering at 300-450 deg.C, and sintering at 700-800 deg.C.
2. The method of claim 1, wherein the ratio of cellular ferric phosphate to lithium source is 1: (1-1.1), wherein the lithium source is selected from one or a mixture of two of lithium hydroxide and lithium carbonate.
3. The method for preparing the ceramic tile according to claim 1, wherein the sand milling adopts a high-energy ball milling mode, and the ball milling time is 1-4 hours; the particle size D50 of the dispersion is 200-300nm.
4. The method according to claim 1, wherein the protective atmosphere is one or a mixture of two or more selected from the group consisting of high purity nitrogen, high purity helium, and high purity argon having a purity of more than 99.999%.
5. The method of producing according to claim 1, wherein the layered Li-Al double metal hydroxide has an interlayer spacing of 0.1 to 1.5nm.
6. A low temperature lithium iron phosphate positive electrode material, characterized in that it is produced by the production method according to any one of claims 1 to 5.
7. A lithium ion battery comprising a positive electrode, wherein the active material of the positive electrode comprises the low temperature lithium iron phosphate positive electrode material of claim 6.
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