CN112133900A - Positive electrode active material and lithium ion battery containing the same - Google Patents
Positive electrode active material and lithium ion battery containing the same Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 37
- 239000007774 positive electrode material Substances 0.000 title abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 64
- 239000011572 manganese Substances 0.000 claims abstract description 56
- 239000000203 mixture Substances 0.000 claims abstract description 43
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 29
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 claims abstract description 28
- 229910021450 lithium metal oxide Inorganic materials 0.000 claims abstract description 20
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 229910015944 LiMn0.8Fe0.2PO4 Inorganic materials 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 6
- 229910015835 LiMn0.65Fe0.35PO4 Inorganic materials 0.000 claims description 2
- 229910015831 LiMn0.6Fe0.4PO4 Inorganic materials 0.000 claims description 2
- 229910015862 LiMn0.75Fe0.25PO4 Inorganic materials 0.000 claims description 2
- 229910015855 LiMn0.7Fe0.3PO4 Inorganic materials 0.000 claims description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 239000010405 anode material Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000011267 electrode slurry Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229910052493 LiFePO4 Inorganic materials 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910010199 LiAl Inorganic materials 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 238000005056 compaction Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 230000005536 Jahn Teller effect Effects 0.000 description 2
- 229910000668 LiMnPO4 Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- -1 lithium iron manganese phosphate compound Chemical class 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000010450 olivine Substances 0.000 description 2
- 229910052609 olivine Inorganic materials 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910011917 LiFe1-z Inorganic materials 0.000 description 1
- 229910014985 LiMnxFe1-xPO4 Inorganic materials 0.000 description 1
- 229910014982 LiMnxFe1−xPO4 Inorganic materials 0.000 description 1
- DOCYQLFVSIEPAG-UHFFFAOYSA-N [Mn].[Fe].[Li] Chemical compound [Mn].[Fe].[Li] DOCYQLFVSIEPAG-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 238000007599 discharging Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
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- 238000005755 formation reaction Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
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- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- 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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A positive electrode active material and a lithium ion battery containing the same are disclosed. The positive electrode active material is a mixture including lithium metal oxide particles having the formula: LiM2‑xMnxOrWherein x is 0. ltoreq. x < 2, and r is a metal satisfying the above conditionThe amount of oxygen element with chemical valence of oxide, M is selected from one or more elements of Ni, Cr, Fe, Al, Mg, Cu, Ti, Zn, Ca and Co; and lithium iron manganese phosphate particles having the formula: liyFe1‑zMnzPO4Wherein y is more than or equal to 1 and less than or equal to 1.10, and z is more than or equal to 0.5 and less than 1; if n is the number of moles of Mn element in the mixture (the valence state of Mn is more than or equal to + 3)/the number of moles of Fe element in the mixture (the valence state of Fe is more than + 2), n is more than 0 and less than or equal to 500; if m is the ratio of the value of the particle diameter D50 of the particles of the component (a) to the value of the particle diameter D50 of the particles of the component (b), then m is not less than 1 but not more than 95.
Description
Technical Field
The invention relates to a positive electrode material mixture which can be used for preparing a positive electrode of a lithium ion battery. The invention also relates to a positive electrode prepared from the positive electrode material mixture and a lithium ion battery containing the positive electrode.
Background
With extensive and intensive research by researchers for many years, the performance of the lithium iron phosphate anode material is continuously improved. LiFePO4The cathode material has a series of advantages of good safety performance and thermal stability, rich raw material sources, no precious metal, low process cost and the like, and is one of the most widely applied cathode materials in the field of lithium ion batteries.
However, LiFePO4The low voltage platform of 3.4V and the lower gram capacity of the anode material limit the universality of the application field. LiMnPO4Has a higher voltage platform and has the same performance as LiFePO4Similar olivine structure, but poor electronic conductivity and diffusivity, difficult to synthesize and apply on a large scale. Researchers in LiMnPO by combining the advantages of the LiMnPO and the LiMnPO4Doping Fe element to obtain LiFe1-zMnzPO4A solid solution material. The theoretical gram capacity of the lithium iron manganese phosphate is similar to that of the lithium iron phosphate (170mAh/g), but the voltage platform of the lithium iron manganese phosphate is 4.0V-4.1V, which is higher than that of LiFePO4The voltage platform of 3.4V has a weight energy density higher than that of LiFePO4The height is about 15 percent. Its higher voltage plateau corresponds to Mn+2/Mn+3A redox couple. The high-voltage platform of the lithium iron manganese phosphate can be blended with high-voltage anode materials such as ternary anode materials and the like, so that the safety and the thermal stability of the high-energy-density lithium battery are improved, and the cost of the ion battery is reduced.
LiMr/2-xMnxOrAnd the positive electrode materials containing + 3-valence Mn elements are influenced by Jahn-Teller effect in the charging and discharging processes, the + 3-valence Mn is disproportionated at a place with low discharge voltage, the + 2-valence Mn is dissolved, and the high-temperature cycle of the materials is poor. Although the voltage plateau of the cathode material is high, the capacity fading caused by the unstable structure due to the dissolution of the Mn element, particularly the poor high temperature cycle, has prevented the wide application of the material. Therefore, the lithium iron manganese phosphate anode material with the same higher voltage platform can be mixed with the lithium metal oxide containing the + 3-valent Mn element, the Jahn-Teller effect influence is reduced, and the high-temperature cycle and the battery safety are improved. The particle size ratio of the two anode materials is further regulated, and the small-particle-size lithium manganese iron phosphate is used as a filler and filled in gaps among lithium metal oxide particles, so that the space utilization rate inside the pole piece and the compaction density of the pole piece are improved.
Chinese patent CN105470495A discloses a positive active material containing nickel-cobalt-manganese-lithium oxide and a composite of formula LiMnxFe1-xPO4The lithium iron manganese phosphate compound comprises particles coated on the surfaces of nickel-cobalt-manganese-lithium oxide particles and embedded in gaps among the particles of the nickel-cobalt-manganese-lithium oxide, the average particle size of the particles of the lithium iron manganese phosphate compound is 30-200nm, and the average particle size of the particles of the nickel-cobalt-manganese-lithium oxide is 10-20000 nm.
There is also a need in the art to provide a positive electrode material with which lithium ion batteries can be made having improved discharge capacity ratios and high temperature cycle life.
Disclosure of Invention
The invention aims to provide a positive electrode material, and a lithium ion battery prepared from the positive electrode material has improved discharge capacity ratio and high-temperature cycle life.
Accordingly, one aspect of the present invention is directed to a mixture for a positive electrode of a lithium ion battery, comprising:
a) lithium metal oxide particles represented by the following formula (1):
LiMxMn2-xOr (1)
wherein x is 0. ltoreq. x < 2, and r is the amount of oxygen element satisfying the chemical valence of the lithium metal oxide;
m is selected from one or more elements of Ni, Cr, Fe, Al, Mg, Cu, Ti, Zn, Ca and Co;
b) lithium iron manganese phosphate particles represented by the following formula (2):
LiyFe1-zMnzPO4 (2)
wherein y is more than or equal to 1 and less than or equal to 1.10, and z is more than or equal to 0.5 and less than 1;
if n is the number of moles of Mn element in the mixture (the valence state of Mn is more than or equal to + 3)/the number of moles of Fe element in the mixture (the valence state of Fe is + 2), n is more than 0 and less than 500;
if m is the ratio of the value of the particle diameter D50 of the particles of the component (a) to the value of the particle diameter D50 of the particles of the component (b), then m is not less than 1 but not more than 95.
Another aspect of the invention relates to a positive electrode for a lithium ion battery comprising the above mixture of the invention.
Yet another aspect of the present invention relates to a lithium ion battery comprising the above-described lithium ion battery positive electrode of the present invention.
Drawings
The invention is further described below with reference to the accompanying drawings. In the drawings:
FIG. 1 is a graph of the electrochemical performance of the cell of example 2;
fig. 2 is a graph of electrochemical performance of the cell of comparative example 1.
Detailed Description
The mixture for a positive electrode of a lithium ion battery of the present invention includes lithium metal oxide particles having the following formula (1):
LiMxMn2-xOr (1)
wherein x is 0. ltoreq. x < 2, and r is the amount of oxygen satisfying the chemical valence of the lithium metal oxide
X is 0. ltoreq. x < 2, preferably 0.01. ltoreq. x.ltoreq.1.8, more preferably 0.02. ltoreq. x.ltoreq.1.5, preferably 0.03. ltoreq. x.ltoreq.1.0;
m is selected from one or more elements of Ni, Cr, Fe, Al, Mg, Cu, Ti, Zn, Ca and Co.
In one embodiment of the invention, the lithium metal oxide particles are selected from LiAl0.05Mn1.95O4、LiAl0.02Mn1.98O4、LiZn0.05Mn1.95O4、LiCo0.05Mn1.95O4And the like.
The lithium metal oxide particles of the present invention are commercially available.
In one embodiment of the present invention, the D50 particle size of the lithium oxide particles of the present invention is 30-19000nm, preferably 100-18000nm, more preferably 500-17000nm, and preferably 1000-16000 nm.
The mixture for a positive electrode of a lithium ion battery of the present invention includes lithium iron manganese phosphate particles represented by the following formula (2):
LiyFe1-zMnzPO4 (2)
wherein y is more than or equal to 1 and less than or equal to 1.10, preferably more than or equal to 1 and less than or equal to 1.05;
z is 0.5. ltoreq. z < 1, preferably 0.55. ltoreq. z.ltoreq.0.95, more preferably 0.6. ltoreq. z.ltoreq.0.9, most preferably 0.65. ltoreq. z.ltoreq.0.85.
In one embodiment of the invention, the lithium iron manganese phosphate particles are selected from LiMn0.8Fe0.2PO4、LiMn0.75Fe0.25PO4、LiMn0.7Fe0.3PO4、LiMn0.65Fe0.35PO4、LiMn0.6Fe0.4PO4、LiMn0.55Fe0.45PO4And the like.
In one embodiment of the present invention, the lithium iron manganese phosphate is LiMn0.8Fe0.2PO4。
In one embodiment of the present invention, the particle size of D50 of the lithium iron manganese phosphate particles of the present invention is 30-15000nm, preferably 100-12000nm, more preferably 500-10000nm, and preferably 1000-5000 nm.
The mixture for the positive electrode of the lithium ion battery is a particle mixture formed by lithium metal oxide particles shown in a formula (1) and lithium manganese iron phosphate particles shown in a formula (2).
If n is the number of moles of Mn in the mixture (the valence state of Mn is +3) or the number of moles of Fe in the mixture (the valence state of Fe is + 2), then n is 0 < 500, preferably 1. ltoreq. n.ltoreq.400, more preferably 2. ltoreq. n.ltoreq.300, preferably 3. ltoreq. n.ltoreq.200, most preferably 4. ltoreq. n.ltoreq.100, and most preferably 5. ltoreq. n.ltoreq.50.
If m is the ratio of the value of the particle size D50 of the particles of component (a) to the value of the particle size D50 of the particles of component (b), then 1. ltoreq. m.ltoreq.95, preferably 1.5. ltoreq. m.ltoreq.90, more preferably 2. ltoreq. m.ltoreq.85, preferably 2.5. ltoreq. m.ltoreq.80, particularly preferably 3. ltoreq. m.ltoreq.75, particularly preferably 3.5. ltoreq. m.ltoreq.70.
In one embodiment of the invention, the lithium iron manganese phosphate particles have a specific surface area of less than 25m2A ratio of/g, preferably less than 22m2A/g, more preferably less than 20m2A ratio of/g, preferably less than 18m2A/g, preferably less than 15m2/g。
The method for producing the mixture for a positive electrode of a lithium ion battery of the present invention is not particularly limited, and may be a conventional method known in the art. For example, lithium-containing oxide particles and lithium iron manganese phosphate particles may be mixed as required.
Another aspect of the invention relates to a positive electrode for a lithium ion battery comprising the above mixture of the invention.
The method for producing the positive electrode of the lithium ion battery of the present invention is not particularly limited, and may be a conventional method known in the art. In one example of the present invention, the manufacturing method includes dispersing the above-described mixture for a positive electrode of a lithium ion battery of the present invention, a binder, and a conductive agent in an oil-based solvent to prepare a positive electrode slurry. Wherein, the proportion of the anode material mixture is 80-98%, the proportion of the binder is 1-10%, and the proportion of the conductive agent is 1-10%.
In one embodiment of the present invention, the conductive agent is one or more of carbon nanotube, conductive graphite, conductive carbon black, acetylene black, graphene, and carbon fiber.
In one example of the present invention, the binder used in the positive electrode slurry is polyvinylidene fluoride.
In one example of the present invention, the oil-based solvent used in the positive electrode slurry is N-methylpyrrolidone.
Yet another aspect of the present invention relates to a lithium ion battery comprising the above-described lithium ion battery positive electrode of the present invention.
In one embodiment of the invention, the average discharge voltage of the lithium ion battery manufactured by using the cathode material mixture is greater than or equal to 3.6V.
The invention adopts two anode materials of lithium metal oxide particles and lithium iron manganese phosphate particles to be mixed as active substances of an anode piece. Because the lithium iron manganese phosphate has a relatively stable olivine structure, the + 3-valent Mn element and the Fe element are not easy to separate out. In the circulation process, particularly in the high-temperature circulation process, the lithium manganese iron phosphate can keep better structural stability and integrity. Meanwhile, the button half-cell discharge voltage platform of the lithium manganese iron phosphate is 4.0V-4.1V, has higher energy density, and can be well compounded with the discharge voltage platform of lithium metal oxide containing + 3-valent Mn element. The lithium metal oxide containing the + 3-valent Mn element is generally a spinel or a layered structure, wherein the + 3-valent Mn element is easy to disproportionate to cause structural instability or structural collapse, so that the rapid attenuation of the circulating capacity is caused. By mixing lithium iron manganese phosphate and lithium metal oxide, the proportion of + 3-valent Mn element and + 2-valent Fe element in the mixture of the lithium iron manganese phosphate and the lithium metal oxide is regulated and controlled, and the influence of structural change caused by disproportionation of Mn element in the lithium metal oxide is reduced. Meanwhile, the particle size ratio of the lithium iron manganese phosphate and the lithium iron manganese phosphate is further regulated, and the lithium iron manganese phosphate with small particle size is used as a filler and filled in gaps among lithium metal oxide particles, so that the space utilization rate inside the pole piece is improved.
Examples
The present invention will be described in further detail with reference to examples, which are merely illustrative and are not to be construed as limiting the present invention.
Example 1
LiAl was used as the positive electrode material mixture in the present example0.05Mn1.95O4(D50 particle size 12 μm) and LiMn0.8Fe0.2PO4(D50 particle size 2 μm), mixtureThe ratio n of the number of moles of the medium Mn element (the valence of Mn is more than or equal to +3) to the number of moles of the Fe element in the mixture (the valence of Fe is more than + 2) is 17.37, and LiAl0.05Mn1.95O4And LiMn0.8Fe0.2PO4The ratio m of the D50 values of the two particles is 6, and the specific surface area of the lithium iron manganese phosphate particles is 15m2/g。
The positive electrode slurry in the embodiment comprises the following components and proportions, by weight, based on the total solid weight, a positive electrode material mixture accounts for 97 wt%, a conductive agent comprises 1 wt% of conductive carbon black and 0.5 wt% of carbon nanotubes, a binder comprises 1.5 wt% of polyvinylidene fluoride, and a slurry solvent uses N-methyl pyrrolidone.
Preparing a positive electrode: polyvinylidene fluoride (PVDF) and part of N-methyl pyrrolidone (NMP) are placed in a mixer to be stirred at low speed for 24 hours to prepare glue solution with 6 percent of PVDF content. And then adding conductive carbon black and a carbon nano tube solution into the glue solution, stirring at a low speed firstly, and then stirring at a high speed for 1 h. Adding LiAl secondly0.05Mn1.95O4And LiMn0.8Fe0.2PO4And stirring the anode material at a low speed for 1 hour, and then stirring at a high speed for 2 hours. Finally, stir at low speed overnight. After the slurry is vacuumed, bubbles are removed and the fineness is tested, the slurry is uniformly coated on an aluminum foil, and the anode plate is prepared by baking the slurry in an oven at 115 ℃ and rolling and slitting the anode plate. The surface density of the pole piece is 20mg/cm2。
Preparing a negative electrode: adding artificial graphite, an adhesive and conductive carbon black into a water solvent, and stirring into uniform negative electrode slurry in a mixer; and uniformly coating the negative electrode slurry on a copper foil, drying at 90 ℃, and rolling and slitting to obtain a negative electrode sheet.
Preparing a battery: and (3) placing the prepared positive pole piece and the prepared negative pole piece on an automatic laminating machine, and using a PE diaphragm with the thickness of 20um to finish the manufacture of the battery cell. And wrapping the battery core by using an aluminum plastic film, and preparing a finished battery after battery liquid injection, packaging, formation, aging and capacity grading.
Example 2
In this example, the mixture except for the positive electrode material was LiAl0.05Mn1.95O4And LiMn0.8Fe0.2PO4The ratio n of the number of moles of Mn element in the mixture (the valence of Mn is +3) to the number of moles of Fe element in the mixture (the valence of Fe is + 2) is 10.13, and the rest is the same as in example 1.
The electrochemical performance profile of the thus-prepared battery was tested, and the results are shown in fig. 1.
Example 3
In this example, the mixture except for the positive electrode material was LiAl0.05Mn1.95O4And LiMn0.8Fe0.2PO4The ratio n of the number of moles of Mn element in the mixture (the valence of Mn is +3) to the number of moles of Fe element in the mixture (the valence of Fe is + 2) is 6.51, and the rest is the same as in example 1.
Comparative example 1
In this comparative example, the cathode material was LiAl0.05Mn1.95O4Otherwise, the contents are the same as in example 1, that is, the lithium iron manganese phosphate particles are not added in this comparative example.
The electrochemical performance profile of the thus-prepared battery was tested, and the results are shown in fig. 2.
Comparative example 2
LiAl was used as the positive electrode material mixture in the present example0.05Mn1.95O4And LiMn0.8Fe0.2PO4The ratio n of the number of moles of Mn element in the mixture (the valence of Mn is more than or equal to +3) to the number of moles of Fe element in the mixture (the valence of Fe is more than + 2) is 17.37, and LiAl0.05Mn1.95O4And LiMn0.8Fe0.2PO4The ratio m of the D50 values for the two particles was 0.8. The rest is the same as in example 1.
The prepared pouch batteries of examples 1-3 and comparative examples 1-2 were used to test the compaction density of the positive electrode plate, the gram capacity of the pouch battery, and the high temperature cycle performance at 45 ℃.
The results of the experiment are shown in table 1. In LiAl0.05Mn1.95O4The gram capacity of the anode material of the lithium ion battery can be improved by adding the lithium manganese iron phosphateHigh temperature cycle life. It can be seen from comparing example 1 and comparative example 2 that the ratio of the D50 particle sizes of the two materials has a large effect on the compacted density and high temperature cycle life of the lithium ion battery. Lithium ion batteries with a ratio of D50 values of m 0.8 have lower material compaction densities and lower high temperature cycle life than lithium ion batteries with m 6.
Table 1 results of cell performance test of examples 1 to 4 and comparative example 1
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (9)
1. A mixture for a positive electrode of a lithium ion battery, comprising:
a) lithium metal oxide particles represented by the following formula (1):
LiMxMn2-xOr (1)
wherein x is 0. ltoreq. x < 2, and r is the amount of oxygen element satisfying the chemical valence of the lithium metal oxide;
m is selected from one or more elements of Ni, Cr, Fe, Al, Mg, Cu, Ti, Zn, Ca and Co;
b) lithium iron manganese phosphate particles represented by the following formula (2):
LiyFe1-zMnzPO4 (2)
wherein y is more than or equal to 1 and less than or equal to 1.10, and z is more than or equal to 0.5 and less than 1;
if n is the number of moles of Mn element in the mixture, the valence state of Mn is more than or equal to + 3/the number of moles of Fe element in the mixture, and the valence state of Fe is +2, n is more than 0 and less than or equal to 500;
if m is the ratio of the value of the particle diameter D50 of the particles of the component (a) to the value of the particle diameter D50 of the particles of the component (b), then m is not less than 1 but not more than 95.
2. The mixture for a positive electrode of a lithium ion battery according to claim 1, wherein 0.01. ltoreq. x.ltoreq.1.8, more preferably 0.02. ltoreq. x.ltoreq.1.5, preferably 0.03. ltoreq. x.ltoreq.1.0.
3. The mixture for a positive electrode of a lithium ion battery according to any one of claims 1 to 3, wherein the D50 particle size of the lithium oxide particles is 30-19000nm, preferably 100-18000nm, more preferably 500-17000nm, preferably 1000-16000 nm.
4. The mixture for a positive electrode of a lithium ion battery according to any one of claims 1 to 3, wherein the particle size D50 of the lithium iron manganese phosphate particles is 30-15000nm, preferably 100-12000nm, more preferably 500-10000nm, preferably 1000-5000 nm.
5. The mixture for a positive electrode of a lithium ion battery according to any of claims 1 to 3, characterized in that 1. ltoreq. n.ltoreq.400, preferably 2. ltoreq. n.ltoreq.300, particularly preferably 3. ltoreq. n.ltoreq.200, preferably 5. ltoreq. n.ltoreq.50.
6. The mixture for a positive electrode of a lithium ion battery according to any of claims 1 to 3, characterized in that 1.5. ltoreq. m.ltoreq.90, preferably 2. ltoreq. m.ltoreq.85, preferably 2.5. ltoreq. m.ltoreq.80, preferably 3. ltoreq. m.ltoreq.75, preferably 3.5. ltoreq. m.ltoreq.70.
7. The mixture for a positive electrode of a lithium ion battery according to any of claims 1 to 3, wherein the lithium metal oxide particles are selected from LiAl0.05Mn1.95O4、LiAl0.05Mn1.95O4、LiAl0.02Mn1.98O4、LiZn0.05Mn1.95O4、LiCo0.05Mn1.95O4One or more of the following materials;
the lithium iron manganese phosphate particles are selected from LiMn0.8Fe0.2PO4、LiMn0.75Fe0.25PO4、LiMn0.7Fe0.3PO4、LiMn0.65Fe0.35PO4、LiMn0.6Fe0.4PO4、LiMn0.55Fe0.45PO4And the like.
8. A positive electrode for a lithium ion battery comprising the mixture for a positive electrode for a lithium ion battery according to any one of claims 1 to 8.
9. A lithium ion battery comprising the positive electrode of the lithium ion battery of claim 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113054157A (en) * | 2021-03-15 | 2021-06-29 | 星恒电源股份有限公司 | Double-composite modified spinel lithium manganate positive plate, preparation method thereof and lithium ion battery |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101009372A (en) * | 2006-01-25 | 2007-08-01 | Nec东金株式会社 | Lithium secondary battery |
| CN101207197A (en) * | 2006-12-22 | 2008-06-25 | 比亚迪股份有限公司 | Lithium ion battery anode material and lithium ion battery and anode containing the material |
| US20140131633A1 (en) * | 2011-07-04 | 2014-05-15 | Nissan Motor Co., Ltd. | Positive electrode active material for electric device, positive electrode for electric device, and electric device |
| CN104134815A (en) * | 2013-07-19 | 2014-11-05 | 中航锂电（洛阳）有限公司 | Mixed positive electrode material and application thereof |
| CN105185987A (en) * | 2014-05-29 | 2015-12-23 | 宁德新能源科技有限公司 | Positive electrode material and lithium ion secondary battery |
| CN105470495A (en) * | 2014-09-05 | 2016-04-06 | 比亚迪股份有限公司 | Positive active material and preparation method thereof, cathode material of lithium ion battery and preparation method thereof, as well as lithium ion battery |
| CN108777298A (en) * | 2018-06-07 | 2018-11-09 | 中国科学院宁波材料技术与工程研究所 | A kind of positive electrode, positive plate and lithium ion battery |
| WO2019204659A1 (en) * | 2018-04-19 | 2019-10-24 | A123 Systems Llc | Method and systems for coated cathode materials and use of coated cathode materials |
| CN111048760A (en) * | 2019-12-18 | 2020-04-21 | 江苏力泰锂能科技有限公司 | Positive electrode active material and method for producing same |
| CN111092194A (en) * | 2018-10-23 | 2020-05-01 | 宁德时代新能源科技股份有限公司 | Positive pole piece, preparation method thereof and lithium ion secondary battery |
-
2020
- 2020-09-27 CN CN202011033821.7A patent/CN112133900A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101009372A (en) * | 2006-01-25 | 2007-08-01 | Nec东金株式会社 | Lithium secondary battery |
| CN101207197A (en) * | 2006-12-22 | 2008-06-25 | 比亚迪股份有限公司 | Lithium ion battery anode material and lithium ion battery and anode containing the material |
| US20140131633A1 (en) * | 2011-07-04 | 2014-05-15 | Nissan Motor Co., Ltd. | Positive electrode active material for electric device, positive electrode for electric device, and electric device |
| CN104134815A (en) * | 2013-07-19 | 2014-11-05 | 中航锂电（洛阳）有限公司 | Mixed positive electrode material and application thereof |
| CN105185987A (en) * | 2014-05-29 | 2015-12-23 | 宁德新能源科技有限公司 | Positive electrode material and lithium ion secondary battery |
| CN105470495A (en) * | 2014-09-05 | 2016-04-06 | 比亚迪股份有限公司 | Positive active material and preparation method thereof, cathode material of lithium ion battery and preparation method thereof, as well as lithium ion battery |
| WO2019204659A1 (en) * | 2018-04-19 | 2019-10-24 | A123 Systems Llc | Method and systems for coated cathode materials and use of coated cathode materials |
| CN108777298A (en) * | 2018-06-07 | 2018-11-09 | 中国科学院宁波材料技术与工程研究所 | A kind of positive electrode, positive plate and lithium ion battery |
| CN111092194A (en) * | 2018-10-23 | 2020-05-01 | 宁德时代新能源科技股份有限公司 | Positive pole piece, preparation method thereof and lithium ion secondary battery |
| CN111048760A (en) * | 2019-12-18 | 2020-04-21 | 江苏力泰锂能科技有限公司 | Positive electrode active material and method for producing same |
Non-Patent Citations (1)
| Title |
|---|
| ANDREAS KLEIN, ET AL.: ""Origin of the Synergetic Effects of LiFe0.3Mn0.7PO4 – Spinel Blends via Dynamic In Situ X-ray Diffraction Measurements"", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113054157A (en) * | 2021-03-15 | 2021-06-29 | 星恒电源股份有限公司 | Double-composite modified spinel lithium manganate positive plate, preparation method thereof and lithium ion battery |
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