CN113471414A - Lithium ion battery composite positive electrode material and preparation method and application thereof - Google Patents
Lithium ion battery composite positive electrode material and preparation method and application thereof Download PDFInfo
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- CN113471414A CN113471414A CN202010244340.4A CN202010244340A CN113471414A CN 113471414 A CN113471414 A CN 113471414A CN 202010244340 A CN202010244340 A CN 202010244340A CN 113471414 A CN113471414 A CN 113471414A
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- Prior art keywords
- lithium
- equal
- composite
- ion battery
- positive electrode
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- 239000002131 composite material Substances 0.000 title claims abstract description 171
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000007774 positive electrode material Substances 0.000 title claims description 57
- 239000000463 material Substances 0.000 claims abstract description 72
- 239000011247 coating layer Substances 0.000 claims abstract description 55
- 239000010416 ion conductor Substances 0.000 claims abstract description 54
- 239000010410 layer Substances 0.000 claims abstract description 53
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 53
- 239000010405 anode material Substances 0.000 claims abstract description 50
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000011532 electronic conductor Substances 0.000 claims abstract description 36
- 239000010406 cathode material Substances 0.000 claims abstract description 30
- 239000004020 conductor Substances 0.000 claims abstract description 20
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 8
- 239000011029 spinel Substances 0.000 claims abstract description 8
- 238000005253 cladding Methods 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims description 58
- 239000011248 coating agent Substances 0.000 claims description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 53
- 239000011572 manganese Substances 0.000 claims description 53
- 238000000034 method Methods 0.000 claims description 48
- 150000001875 compounds Chemical class 0.000 claims description 43
- 239000002243 precursor Substances 0.000 claims description 40
- 229910019142 PO4 Inorganic materials 0.000 claims description 35
- 239000007788 liquid Substances 0.000 claims description 34
- 229920001940 conductive polymer Polymers 0.000 claims description 23
- 229910021389 graphene Inorganic materials 0.000 claims description 22
- -1 polyphenylene ethylene Polymers 0.000 claims description 22
- 238000001354 calcination Methods 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 19
- 239000002041 carbon nanotube Substances 0.000 claims description 19
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 19
- 239000012298 atmosphere Substances 0.000 claims description 14
- 229910002804 graphite Inorganic materials 0.000 claims description 14
- 239000010439 graphite Substances 0.000 claims description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 14
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 13
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 11
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 11
- 229910010092 LiAlO2 Inorganic materials 0.000 claims description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims description 10
- 230000002194 synthesizing effect Effects 0.000 claims description 10
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 9
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 9
- 229910011131 Li2B4O7 Inorganic materials 0.000 claims description 9
- 229910007562 Li2SiO3 Inorganic materials 0.000 claims description 9
- 229910007822 Li2ZrO3 Inorganic materials 0.000 claims description 9
- 229910011790 Li4GeO4 Inorganic materials 0.000 claims description 9
- 229910011899 Li4SnS4 Inorganic materials 0.000 claims description 9
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 claims description 9
- 229910011201 Li7P3S11 Inorganic materials 0.000 claims description 9
- 229910003327 LiNbO3 Inorganic materials 0.000 claims description 9
- 229910012463 LiTaO3 Inorganic materials 0.000 claims description 9
- 229910010252 TiO3 Inorganic materials 0.000 claims description 9
- 239000004917 carbon fiber Substances 0.000 claims description 9
- 229910003472 fullerene Inorganic materials 0.000 claims description 9
- 229910052909 inorganic silicate Inorganic materials 0.000 claims description 9
- 229910000921 lithium phosphorous sulfides (LPS) Inorganic materials 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 claims description 9
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- 229910001338 liquidmetal Inorganic materials 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 claims description 4
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 4
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 4
- 229920000128 polypyrrole Polymers 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- YWJVFBOUPMWANA-UHFFFAOYSA-H [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YWJVFBOUPMWANA-UHFFFAOYSA-H 0.000 claims description 3
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- 229910052786 argon Inorganic materials 0.000 claims description 3
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- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- SBWRUMICILYTAT-UHFFFAOYSA-K lithium;cobalt(2+);phosphate Chemical compound [Li+].[Co+2].[O-]P([O-])([O-])=O SBWRUMICILYTAT-UHFFFAOYSA-K 0.000 claims description 3
- 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 description 3
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- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 claims description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 27
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- 230000002195 synergetic effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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Abstract
The invention discloses a lithium ion battery composite anode material and a preparation method and application thereof, belonging to the technical field of lithium ion battery anode materials. The lithium ion battery composite anode material comprises an anode base material, and a poor lithium intermediate layer and a composite coating layer which are sequentially coated on the surface of the anode base material; the lithium-poor intermediate layer is Li with a spinel structurexMx1Mn2‑x1O4Said composite coating layer comprising electricityA sub-conductor and an ion conductor; the lithium ion battery is obtained by cladding a composite cladding layer consisting of a spinel-structured lithium-poor intermediate layer, an electronic conductor and an ionic conductor on the surface of a positive electrode base material in a composite way. According to the composite cathode material, the cathode base material is coated by the lithium-poor intermediate layer and the composite coating layer, so that the rate capability and the coulombic efficiency of the composite cathode material are effectively improved, and the cycle performance of the composite cathode material is improved.
Description
Technical Field
The invention relates to the technical field of lithium ion battery anode materials, in particular to a lithium ion battery composite anode material and a preparation method and application thereof.
Background
Currently, lithium ion batteries have been widely used in the fields of consumer electronics, energy storage devices, power tools, and the like. The cathode material is one of core materials of the lithium ion battery, and a lot of researches are carried out aiming at different application fields, and at present, commercial cathode materials mainly comprise lithium cobaltate, lithium iron phosphate, lithium manganate, lithium nickel cobalt manganese and lithium nickel cobalt aluminate. The above cathode materials have more or less surface interface problems in lithium ion batteries, for example, the electrolyte and the surface of the cathode material generate side reactions, and the interface resistance between the solid electrolyte and the cathode material is large. The existence of the surface interface problem is closely related to the stability of the surface of the positive electrode material, the ion transfer and electron transfer characteristics, the surface reaction, the surface residual lithium and the like, and also has a great relationship with the compatibility between the surface of the positive electrode material and the electrolyte. Therefore, how to construct a suitable surface interface on the positive electrode material is an important research field.
The surface coating of the positive electrode material is one of means for effectively improving the surface interface problem. At present, the surface coating method of the anode material generally comprises the following steps: firstly, metal oxide can be coated on the surface of a positive electrode material, and then a stable coating layer is formed through annealing, the coating method can well isolate the side reaction between the positive electrode material and an electrolyte, but the coating amount cannot be too large, otherwise, the electrochemical performance of the positive electrode material is greatly influenced; the other method is to coat the fast ion conductor on the surface of the anode material, which has good help effect on the ion conduction of the material surface, but the electron conductance of the fast ion conductor is generally poor, and the coating amount is not too large; there is also a method of coating the surface of the positive electrode material with an electrochemically active material, which does not degrade the performance of the material or even improve it to some extent, but the surface-coated electrochemically active material still causes a new surface interface problem due to its activity.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a composite anode material of a lithium ion battery, the composite anode material coats an anode base material through a lithium-poor intermediate layer and a composite coating layer, the rate capability and the coulombic efficiency of the anode material are effectively improved, and the cycle performance of the anode material is improved.
The invention also aims to provide a preparation method of the composite cathode material of the lithium ion battery.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a lithium ion battery composite anode material comprises an anode base material, and a lithium-poor intermediate layer and a composite coating layer which are sequentially coated on the surface of the anode base material; the lithium-poor intermediate layer is Li with a spinel structurexMx1Mn2-x1O4Wherein 0 is less than or equal to x<2，0≤x1<2, M is one or more of Ni, V, Co, Cr, Cu, Fe, Mo, Al, La, Mg, Ca, Ge, Gd and B; the composite cladding layer comprises an electron conductor and an ion conductor.
In a preferred embodiment of the present invention, the lithium-poor intermediate layer accounts for 0.01 to 15% by mass of the lithium ion battery composite positive electrode material.
In a preferred embodiment of the present invention, the positive electrode base material is at least one of lithium iron phosphate, lithium manganese iron phosphate, lithium cobalt phosphate, lithium vanadium phosphate, lithium cobalt oxide, lithium nickelate, lithium manganate, lithium nickel cobalt aluminate, lithium nickel manganate, and a lithium-rich layered oxide.
In a preferred embodiment of the present invention, the composite coating layer accounts for 0.01 to 40% by mass of the composite positive electrode material for a lithium ion battery.
As a preferred embodiment of the present invention, the electronic conductor is one or more of amorphous carbon, conductive graphite, nanographite, conductive carbon black, carbon nanotube, carbon fiber, fullerene, graphene, conductive polymer or partially carbonized conductive polymer.
As a preferred embodiment of the present invention, the conductive polymer is selected from at least one of polyacetylene, polythiophene, polypyrrole, polyaniline, polyphenylene ethylene, or polydiyne.
As a preferred embodiment of the present invention, the ion conductor comprises Li1+aAlaGe2-a(PO4)3、Li3bLa2/3- bTiO3、LiZr2-cTic(PO4)3、Li1+yAlyTi2-y(PO4)3、Li4-zGe1-zPzS4、Li7-2n-mM’nLa3Zr2-mM”mO12、Li7P3S11、Li3PS4、Li3PO4、Li4P2O7、LiPO3、Li3BO3、Li2B4O7、Li2ZrO3、LiAlO2、LiNbO3、Li4SnS4、Li4Ti5O12、Li4SiO4、Li2SiO3、LiTaO3、Li2CO3、Li4GeO4One or more of LiF; wherein a is more than or equal to 0 and less than or equal to 2, b is more than or equal to 0 and less than or equal to 2/3, c is more than or equal to 0 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 2, z is more than or equal to 0 and less than or equal to 1, n is more than or equal to 0 and less than or equal to 3, M is more than or equal to 0 and less than or equal to 2, M 'is at least one of Ge and Al, and M' is one or more of Nb, Ta, Te and W.
In a preferred embodiment of the present invention, the median particle diameter D of the positive electrode base material50Not more than 30 μm; the thickness of the lithium-poor intermediate layer is not more than 500 nm; the thickness of the composite coating layer is not more than 5 mu m.
A preparation method of a composite anode material of a lithium ion battery comprises the following steps:
s1, coating the lithium-poor intermediate layer precursor on the positive electrode base material to obtain a first compound; calcining the first compound at 300-1200 ℃ for 0.1-30 h to obtain a positive electrode material coating of the poor lithium intermediate layer coating positive electrode base material;
s2, dispersing the electron conductor precursor and the ion conductor precursor in a liquid reagent, adding the anode material coating prepared in the step S1, and coating the electron conductor precursor and the ion conductor precursor on the anode material coating to obtain a second compound; and calcining the second compound in an inert atmosphere at 50-1200 ℃ for 0.1-30 h to obtain the lithium ion battery composite anode material with the lithium-poor intermediate layer and the composite coating layer coating the anode base material.
In a preferred embodiment of the present invention, the lithium-poor interlayer precursor in step S1 is LixMx1Mn2- x1O4Wherein 0 is less than or equal to x<2，0≤x1<2, M is one or more of Ni, V, Co, Cr, Cu, Fe, Mo, Al, La, Mg, Ca, Ge, Gd and B; or can synthesize LixMx1Mn2-x1O4Corresponding to M, Mn and Li.
As a preferred embodiment of the present invention, the electron conductor precursor in step S2 is one or more of amorphous carbon, conductive graphite, nano-graphite, conductive carbon black, carbon nanotube, carbon fiber, fullerene, graphene, conductive polymer or partially carbonized conductive polymer; or a corresponding substance capable of synthesizing amorphous carbon, conductive graphite, nanographite, conductive carbon black, carbon nanotubes, carbon fibers, fullerenes, graphene, conductive polymers or partially carbonized conductive polymers.
In a preferred embodiment of the present invention, the ion conductor precursor in step S2 is Li1+aAlaGe2-a(PO4)3、Li3bLa2/3-bTiO3、LiZr2-cTic(PO4)3、Li1+yAlyTi2-y(PO4)3、Li4-zGe1-zPzS4、Li7-2n-mM’nLa3Zr2-mM”mO12、Li7P3S11、Li3PS4、Li3PO4、Li4P2O7、LiPO3、Li3BO3、Li2B4O7、Li2ZrO3、LiAlO2、LiNbO3、Li4SnS4、Li4Ti5O12、Li4SiO4、Li2SiO3、LiTaO3、Li2CO3、Li4GeO4And one or more of LiF, wherein a is more than or equal to 0 and less than or equal to 2, b is more than or equal to 0 and less than or equal to 2/3, c is more than or equal to 0 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 2, z is more than or equal to 0 and less than or equal to 1, n is more than or equal to 0 and less than or equal to 3, M is more than or equal to 0 and less than or equal to 2, M 'is at least one of Ge and Al, and M' is one or more of Nb, Ta, Te and W; ion conductor precursors or precursors capable of synthesizing Li1+aAlaGe2-a(PO4)3、Li3bLa2/3-bTiO3、LiZr2-cTic(PO4)3、Li1+yAlyTi2-y(PO4)3、Li4-zGe1-zPzS4、Li7-2n-mM’nLa3Zr2-mM”mO12、Li7P3S11、Li3PS4、Li3PO4、Li4P2O7、LiPO3、Li3BO3、Li2B4O7、Li2ZrO3、LiAlO2、LiNbO3、Li4SnS4、Li4Ti5O12、Li4SiO4、Li2SiO3、LiTaO3、Li2CO3、Li4GeO4Or LiF.
As a preferred embodiment of the present invention, the liquid reagent in step S2 is at least one of water, methanol, ethanol, propanol, isopropanol, ethylene glycol, benzyl alcohol, acetic acid, N-methylpyrrolidone, acetone, acetonitrile, tetrahydrofuran, dimethyl carbonate, propylene carbonate, benzene, toluene, xylene, methyl ether, ethyl ether, and ethylene glycol dimethyl ether.
In a preferred embodiment of the present invention, the inert atmosphere in step S2 is one or more of nitrogen, argon, helium, neon, carbon monoxide and carbon dioxide.
The invention also provides an application of the lithium ion battery composite anode material in the preparation of a lithium ion battery, wherein the lithium ion battery is a liquid lithium ion battery, a mixed solid-liquid metal lithium battery, an all-solid lithium ion battery or an all-solid metal lithium battery.
Compared with the prior art, the invention has the beneficial effects that:
the lithium ion battery composite anode material provided by the invention is obtained by cladding the surface of an anode base material in a composite way by a composite cladding layer consisting of a spinel-structured lithium-poor intermediate layer, an electronic conductor and an ionic conductor, and has the following advantages:
(1) the lithium-poor intermediate layer used in the invention is an electrochemical active material with a spinel structure, has a three-dimensional lithium ion transmission channel, is coated on the surface of the anode base material, can improve the ionic conductivity of the surface of the anode base material, can serve as an intermediate medium with high ionic conductivity after being combined with the outer composite coating layer, and prevents elements of an ionic conductor in the anode base material and the composite coating layer from mutually diffusing; in addition, the existence of the poor lithium intermediate layer can eliminate the residual lithium on the surface of the cathode base material to a certain extent, so that the conductivity of the material is improved, and the rate capability and the coulombic efficiency of the composite cathode material are effectively improved;
(2) the electronic conductor adopted in the invention has higher electronic conductivity, the ionic conductor has higher ionic conductivity, and the composite coating of the electronic conductor and the ionic conductor generates good synergistic effect, so that the surface of the anode material has good electronic conductivity and ionic conductivity simultaneously, thereby well improving the coulomb efficiency and the multiplying power performance of the composite anode material;
(3) the composite coating layer coated by the invention not only can well isolate the direct contact between the anode matrix material and the electrolyte, but also has certain elasticity, and provides certain buffer for the volume change of the anode matrix material in the lithium desorption process, so that the cycle performance of the material is improved;
(4) the composite coating layer coated by the invention not only can well infiltrate with the electrolyte and play a role in retaining the electrolyte, but also can well contact and be compatible with the solid electrolyte, so that the compatibility of the composite anode material in a liquid lithium ion battery, a mixed solid-liquid metal lithium battery, an all-solid lithium ion battery and an all-solid metal lithium battery system is also well improved.
Drawings
FIG. 1 is a schematic structural diagram of a composite positive electrode material of a lithium ion battery according to the present invention;
FIG. 2 is an SEM image of the base material of the positive electrode according to example 1 of the present invention;
fig. 3 is an SEM image of the coating of the positive electrode material according to example 1 of the present invention;
FIG. 4 is an SEM image of the composite cathode material of the lithium ion battery prepared in the embodiment 1 of the invention;
FIG. 5 is a first cycle charge and discharge curve diagram of a liquid lithium ion battery prepared by a sample before modification and a sample after modification in example 1 of the present invention;
FIG. 6 is a graph showing rate performance curves of liquid lithium ion batteries respectively manufactured by a sample before modification and a sample after modification in example 1 of the present invention;
fig. 7 is a 100-cycle performance graph of liquid lithium ion batteries respectively prepared by the sample before modification and the sample after modification in example 1 of the present invention.
The reference numbers illustrate: 100. a positive electrode base material; 200. a lithium-deficient intermediate layer; 300. a composite coating layer; 310. an electronic conductor; 320. an ion conductor.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
A composite positive electrode material of a lithium ion battery, as shown in fig. 1, includes a positive electrode base material 100, and a lithium-poor intermediate layer 200 and a composite coating layer 300 sequentially coated on the surface of the positive electrode base material 100; the composite clad 300 includes an electron conductor 310 and an ion conductor 320.
The positive electrode base material is at least one of lithium iron phosphate, lithium manganese phosphate, lithium iron manganese phosphate, lithium cobalt phosphate, lithium vanadium phosphate, lithium cobaltate, lithium nickelate, lithium manganate, lithium nickel cobalt manganese, lithium nickel cobalt aluminate, lithium nickel manganese and lithium-rich layered oxide. Median diameter D of positive electrode base material50Not more than 30 μm, preferably not more than 20 μm.
Li with spinel structure as lithium-poor intermediate layerxMx1Mn2-x1O4Wherein 0 is less than or equal to x<2，0≤x1<2, M is one or more of Ni, V, Co, Cr, Cu, Fe, Mo, Al, La, Mg, Ca, Ge, Gd and B. The mass fraction of the poor lithium intermediate layer in the lithium ion battery composite anode material is 0.01-15%, preferably 0.05-5%. The thickness of the lithium-poor interlayer is not more than 500nm, preferably not more than 50 nm.
The electronic conductor is one or more of amorphous carbon, conductive graphite, nano graphite, conductive carbon black, carbon nano tubes, carbon fibers, fullerene, graphene, conductive polymers or partially carbonized conductive polymers; the conductive polymer includes but is not limited to common conductive polymers and their derivatives, such as polyacetylene, polythiophene, polypyrrole, polyaniline, polyphenylene ethylene, polydiyne, etc. The ion conductor comprises Li1+aAlaGe2-a(PO4)3、Li3bLa2/3-bTiO3、LiZr2-cTic(PO4)3、Li1+yAlyTi2-y(PO4)3、Li4-zGe1-zPzS4、Li7-2n-mM’nLa3Zr2-mM”mO12、Li7P3S11、Li3PS4、Li3PO4、Li4P2O7、LiPO3、Li3BO3、Li2B4O7、Li2ZrO3、LiAlO2、LiNbO3、Li4SnS4、Li4Ti5O12、Li4SiO4、Li2SiO3、LiTaO3、Li2CO3、Li4GeO4And one or more of LiF, wherein a is more than or equal to 0 and less than or equal to 2, b is more than or equal to 0 and less than or equal to 2/3, c is more than or equal to 0 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 2, z is more than or equal to 0 and less than or equal to 1, n is more than or equal to 0 and less than or equal to 3, M is more than or equal to 0 and less than or equal to 2, M 'is at least one of Ge and Al, and M' is one or more of Nb, Ta, Te and W; the ion conductor is in a crystalline state, an amorphous state or a crystalline-amorphous mixed state. The mass fraction of the composite coating layer in the composite anode material of the lithium ion battery is 0.01-40%, preferably 0.1-15%. The thickness of the composite coating is not more than 5 μm, preferably not more than 1 μm.
The invention also provides a preparation method of the lithium ion battery composite anode material, which comprises the following steps:
s1, coating the lithium-poor intermediate layer precursor on the positive electrode base material to obtain a first compound; calcining the first compound at 300-1200 ℃ for 0.1-30 h to obtain a positive electrode material coating of the poor lithium intermediate layer coating positive electrode base material;
s2, dispersing the electron conductor precursor and the ion conductor precursor in a liquid reagent, adding the positive electrode material coating prepared in the step S1, and coating the electron conductor precursor and the ion conductor precursor on the positive electrode material coating to obtain a second compound; and calcining the second compound in an inert atmosphere at 50-1200 ℃ for 0.1-30 h to obtain the lithium ion battery composite anode material with the lithium-poor intermediate layer and the composite coating layer coating the anode base material.
In step S1, the lithium-deficient intermediate layer precursor may be coated on the positive electrode substrate by one or more of a solvothermal method, a chemical vapor deposition method, an evaporation solvent method, an atomic layer deposition method, a spray drying method, a fluidized bed method, a spray method, a sol-gel method, a precipitation method, a ball milling method, a particle fusion method, a magnetron sputtering method, and a pulsed laser deposition method. Some of the above methods require the use of a solvent which is at least one of water, methanol, ethanol, propanol, isopropanol, ethylene glycol, benzyl alcohol, acetic acid, N-methylpyrrolidone, acetone, acetonitrile, tetrahydrofuran, dimethyl carbonate, propylene carbonate, benzene, toluene, xylene, methyl ether, ethyl ether, and ethylene glycol dimethyl ether.
Further, the lithium-deficient intermediate layer precursor in step S1 is LixMx1Mn2-x1O4Or Li can be synthesizedxMx1Mn2-x1O4Corresponding to M, Mn and Li. When the lithium-deficient interlayer precursor is LixMx1Mn2-x1O4When the lithium-deficient intermediate layer precursor has a median particle size of not more than 500nm, preferably not more than 50nm, where 0. ltoreq. x<2，0≤x1<2, M is one or more of Ni, V, Co, Cr, Cu, Fe, Mo, Al, La, Mg, Ca, Ge, Gd and B. Wherein the compound of M is at least one of lithium M, nitrate of M, sulfate of M, methanesulfonate of M, benzenesulfonate of M, benzylsulfonate of M, carbonate of M, oxalate of M, acetate of M, methoxide of M, ethoxide of M, propoxide of M, isopropoxide of M, n-butoxide of M, tert-butoxide of M, acetylacetonate of M, methyl compound of M, ethyl compound of M, propyl compound of M, isopropyl compound of M, n-butyl compound of M, tert-butoxide of M, phenylchemical of M, benzyl compound of M, sulfide of M, hydroxide of M and oxide of M. The Mn compound is selected from the group consisting of lithium Mn oxide, nitrate Mn oxide, sulfate Mn oxide, methanesulfonate Mn oxide, benzenesulfonate Mn oxide, carbonate Mn oxide, oxalate Mn oxide, acetate Mn oxide, methoxide Mn oxide, ethoxide Mn oxide, propoxide Mn oxide, isopropoxide Mn oxide, n-butoxide Mn oxide, tert-butoxide Mn oxide, acetylacetonate Mn oxide, methyl compound Mn oxide, ethyl compound Mn oxide, propyl compound Mn oxide, isopropylated compound Mn oxideThe compound is at least one of a compound of Mn, a compound of Mn tertiary butyl, a compound of Mn phenyl, a compound of Mn benzyl, a sulfide of Mn, a hydroxide of Mn and an oxide of Mn. The compound of Li is at least one of nitrate of Li, sulfate of Li, methanesulfonate of Li, benzenesulfonate of Li, benzylsulfonate of Li, carbonate of Li, oxalate of Li, acetate of Li, methoxide of Li, ethoxide of Li, propoxide of Li, isopropoxide of Li, n-butoxide of Li, t-butoxide of Li, acetylacetonate of Li, methyl compound of Li, ethyl compound of Li, propyl compound of Li, isopropyl compound of Li, n-butyl compound of Li, t-butoxide of Li, phenylchemical of Li, benzyl compound of Li, sulfide of Li, hydroxide of Li and oxide of Li.
Specifically, step S2 can be performed by the following two methods:
the first method is that firstly, an electronic conductor precursor and an ionic conductor precursor are added into a liquid reagent to prepare solution/dispersion liquid/sol; then adding the positive electrode material coating obtained in the step S1, and coating the electronic conductor precursor and the ionic conductor precursor on the positive electrode material coating by at least one of an evaporation solvent method, a sol-gel method, a solvothermal method or a spray drying method to obtain a second compound; and calcining the second compound for 0.1-30 h at 50-1100 ℃ in an inert atmosphere to obtain the lithium ion battery composite anode material with the lithium-poor intermediate layer and the composite coating layer coating the anode base material.
The second method is that firstly, an electronic conductor precursor and an ionic conductor precursor are added into a liquid reagent to prepare solution/dispersion liquid/sol; then preparing the electronic conductor and ionic conductor composite material by a solvothermal method or a sol-gel method, and adding the electronic conductor and ionic conductor composite material into a liquid reagent to prepare composite material slurry/dispersion liquid; adding the positive electrode material coating obtained in the step S1 into the composite material slurry/dispersion liquid, and coating the electronic conductor and ion conductor composite material on the positive electrode material coating by at least one of an evaporation solvent method, a sol-gel method, a solvothermal method or a spray drying method to obtain a second composite; and calcining the second compound for 0.1-30 h at 50-1000 ℃ in an inert atmosphere to obtain the lithium ion battery composite anode material with the lithium-poor intermediate layer and the composite coating layer coating the anode base material.
Wherein, the electronic conductor precursor in step S2 is one or more of amorphous carbon, conductive graphite, nano-graphite, conductive carbon black, carbon nanotube, carbon fiber, fullerene, graphene, conductive polymer or partially carbonized conductive polymer; or a corresponding substance capable of synthesizing amorphous carbon, conductive graphite, nanographite, conductive carbon black, carbon nanotube, carbon fiber, fullerene, graphene, a conductive polymer, or a partially carbonized conductive polymer, such as an organic carbon source capable of synthesizing amorphous carbon, graphene oxide/organic carbon source capable of synthesizing graphene, a corresponding monomer capable of synthesizing a conductive polymer, or the like.
Wherein the ion conductor precursor in step S2 is Li1+aAlaGe2-a(PO4)3、Li3bLa2/3-bTiO3、LiZr2- cTic(PO4)3、Li1+yAlyTi2-y(PO4)3、Li4-zGe1-zPzS4、Li7-2n-mM’nLa3Zr2-mM”mO12、Li7P3S11、Li3PS4、Li3PO4、Li4P2O7、LiPO3、Li3BO3、Li2B4O7、Li2ZrO3、LiAlO2、LiNbO3、Li4SnS4、Li4Ti5O12、Li4SiO4、Li2SiO3、LiTaO3、Li2CO3、Li4GeO4Or LiF, the median particle diameter of the ion conductor precursor is not more than 30 mu m, preferably not more than 500nm, wherein a is not less than 0 and not more than 2, b is not less than 0 and not more than 2/3, c is not less than 0 and not more than 2, 0Y is more than or equal to 2, z is more than or equal to 0 and less than or equal to 1, n is more than or equal to 0 and less than or equal to 3, M is more than or equal to 0 and less than or equal to 2, M 'is at least one of Ge and Al, and M' is one or more of Nb, Ta, Te and W. The ion conductor precursor may also be capable of synthesizing Li1+aAlaGe2-a(PO4)3、Li3bLa2/3-bTiO3、LiZr2-cTic(PO4)3、Li1+yAlyTi2-y(PO4)3、Li4-zGe1-zPzS4、Li7-2n-mM’nLa3Zr2-mM”mO12、Li7P3S11、Li3PS4、Li3PO4、Li4P2O7、LiPO3、Li3BO3、Li2B4O7、Li2ZrO3、LiAlO2、LiNbO3、Li4SnS4、Li4Ti5O12、Li4SiO4、Li2SiO3、LiTaO3、Li2CO3、Li4GeO4Or LiF, e.g. capable of synthesizing Li3PO4Corresponding phosphoric acid/phosphate and Li compounds, etc.
The liquid reagent used in the two methods of step S2 is at least one of water, methanol, ethanol, propanol, isopropanol, ethylene glycol, benzyl alcohol, acetic acid, N-methylpyrrolidone, acetone, acetonitrile, tetrahydrofuran, dimethyl carbonate, propylene carbonate, benzene, toluene, xylene, methyl ether, ethyl ether, and ethylene glycol dimethyl ether. The liquid reagents used in the second method, which are used in two times, may be the same or different.
Wherein, the inert atmosphere in step S2 is one or more of nitrogen, argon, helium, neon, carbon monoxide and carbon dioxide.
The invention also provides an application of the lithium ion battery composite anode material in the preparation of a lithium ion battery, wherein the lithium ion battery is a liquid lithium ion battery, a mixed solid-liquid metal lithium battery, an all-solid lithium ion battery or an all-solid metal lithium battery.
Example 1
A composite anode material of a lithium ion battery comprises an anode base material, and a poor lithium intermediate layer and a composite coating layer which are sequentially coated on the surface of the anode base material. Wherein the positive electrode base material is LiCoO with a median particle diameter of about 12 μm2(i.e., the sample before modification), the SEM image is shown in fig. 2; the lithium-poor interlayer is Li0.8Ni0.5Mn1.5O4The electronic conductor in the composite coating layer is graphene, and the ion conductor is Li3PO4。
The preparation method of the composite anode material of the lithium ion battery comprises the following steps:
s1, coating 1mol of LiCoO with 0.004mol of lithium acetate, 0.0025mol of nickel acetate and 0.0075mol of manganese acetate by a method of evaporating solvent2(97.87g) to obtain a first complex; then calcining the first compound for 5 hours at 850 ℃ in an air atmosphere to obtain the Li of the lithium-poor interlayer0.8Ni0.5Mn1.5O4The SEM image of the anode material coating of the LCO is shown in FIG. 3;
s2, adding 1g of graphene oxide, 0.01mol of phosphoric acid and 0.03mol of lithium hydroxide into 100mL of water, uniformly dispersing, then adding 1mol of the positive electrode material coating obtained in the step S1, and obtaining a second compound by an evaporation solvent method; calcining the second compound at 500 ℃ for 2h in a nitrogen atmosphere to obtain the Li of the lithium-poor interlayer0.8Ni0.5Mn1.5O4Electronic conductor graphene and ion conductor Li3PO4Composite coated LiCoO2Composite positive electrode material (modified sample).
Wherein the mass fraction of the lithium-poor intermediate layer in the composite cathode material is about 0.898%, the mass fraction of the composite coating layer in the composite cathode material is about 2.14%, and the mass fraction of the electron conductor in the composite coating layer is about 46.34%. LiCoO2The SEM image of the composite cathode material is shown in FIG. 4, in which the particles are modifiedAppearance, a coating can be seen on the surface of the particles.
The positive electrode base material before improvement and the composite positive electrode material after improvement are respectively made into pole pieces, and are used as working electrodes to be assembled into a liquid lithium ion battery, a mixed solid-liquid metal lithium battery, an all-solid lithium ion battery and an all-solid metal lithium battery, and the batteries are subjected to charge and discharge tests, wherein the voltage range is 2.8-4.5V, the first discharge specific capacity and the first coulombic efficiency are tested under 0.1C/0.1C, the rate capability is tested under 0.1C/0.1C two weeks, 0.2C/0.2C two weeks, 0.5C/0.5C two weeks, 0.5C/1C two weeks, 1C/1C two weeks, and the cycle capacity retention rate is tested under 1C/1C for 100 weeks, and the results are shown in figures 5-7 and a table 1.
As can be seen from fig. 5, the discharge plateau and the discharge capacity of the liquid lithium ion battery prepared by using the composite cathode material (sample after improvement) of example 1 are improved compared with the liquid lithium ion battery prepared by using the cathode base material (sample before improvement), and the first coulombic efficiency is significantly improved. As can be seen from fig. 6, the rate capability of the liquid lithium ion battery sample prepared by using the composite cathode material improved in example 1 is significantly improved. As can be seen from fig. 7, the cycling performance of the liquid lithium ion battery sample prepared by using the composite cathode material modified in example 1 is also improved.
TABLE 1 comparison of initial specific discharge capacity, initial coulombic efficiency and cycle performance results
As can be seen from table 1, the first discharge capacity, the first coulombic efficiency and the 100-cycle retention rate of the liquid lithium ion battery, the mixed solid-liquid metal lithium battery, the all-solid lithium ion battery and the all-solid metal lithium battery prepared from the composite cathode material improved by the method of the present invention are all improved relative to the cathode base material before the improvement.
Example 2
A composite anode material of a lithium ion battery comprises an anode base material, and a poor lithium intermediate layer and a composite coating layer which are sequentially coated on the surface of the anode base material. Wherein the positive electrode base material is LiCoO with a median particle diameter of about 12 μm2A sample; the lithium-poor interlayer is Li0.8Ni0.5Mn1.5O4The electronic conductor in the composite coating layer is graphene, and the ion conductor is Li3PO4。
The preparation method of the composite anode material of the lithium ion battery comprises the following steps:
s1, coating 1mol of LiCoO with 0.004mol of lithium acetate, 0.0025mol of nickel acetate and 0.0075mol of manganese acetate by a method of evaporating solvent2(97.87g) to obtain a first complex; then calcining the first compound for 5 hours at 850 ℃ in an air atmosphere to obtain the Li of the lithium-poor interlayer0.8Ni0.5Mn1.5O4The SEM image of the anode material coating of the LCO is shown in FIG. 3;
s2, adding 1g of graphene oxide, 0.01mol of phosphoric acid and 0.03mol of lithium hydroxide into 20mL of water, uniformly dispersing, and preparing the electronic conductor (graphene) and the ionic conductor (Li) by using a solvothermal method3PO4) Then adding the composite material into 100mL of ethanol for uniform dispersion to obtain a composite material dispersion liquid; adding 1mol of the positive electrode material coating obtained in the step S1 into the composite material dispersion liquid and obtaining a second composite by an evaporation solvent method; calcining the second compound at 500 ℃ for 2h in a nitrogen atmosphere to obtain the Li of the lithium-poor interlayer0.8Ni0.5Mn1.5O4Electronic conductor graphene and ion conductor Li3PO4Composite coated LiCoO2And (3) compounding the positive electrode material.
Wherein the mass fraction of the lithium-poor intermediate layer in the composite cathode material is about 0.898%, the mass fraction of the composite coating layer in the composite cathode material is about 2.14%, and the mass fraction of the electron conductor in the composite coating layer is about 46.34%.
Performance comparison experiment one:
the composite positive electrode materials prepared in the embodiments 1 to 2 are respectively manufactured into pole pieces, and are used as working electrodes to be assembled into a liquid lithium ion battery, and the battery is subjected to charge and discharge tests, wherein the first discharge specific capacity and the first coulombic efficiency are tested in a voltage range of 2.8 to 4.5V and 0.1C/0.1C, the rate performance is tested in 0.1C/0.1C two weeks, 0.2C/0.2C two weeks, 0.5C/0.5C two weeks, 0.5C/1C two weeks and 1C/1C two weeks, and the cycle capacity retention rate is tested in 100 weeks at 1C/1C, and the results are shown in Table 2.
As can be seen from table 2, when step S2 is performed, the performance of the obtained composite positive electrode material is equivalent by coating the positive electrode material coating material using the first method and the second method.
TABLE 2 comparison of test results for examples 1-2
| Step S2 | Specific capacity of first discharge (mAh/g) | First coulombic efficiency (%) | 100-week cycle maintenance (%) | |
| Example 1 | |
190 | 96.4 | 88 |
| Example 2 | |
190 | 96.3 | 88 |
Example 3:
a composite anode material of a lithium ion battery comprises an anode base material, and a poor lithium intermediate layer and a composite coating layer which are sequentially coated on the surface of the anode base material. Wherein the positive electrode base material is LiCoO having a median particle diameter of about 10 μm2(i.e., as a pre-modified sample); the lithium-poor interlayer is Li0.7Ni0.4Co0.1Mn1.5O4The electronic conductor in the composite coating layer is a carbon nano tube, and the ionic conductor is LiZr2(PO4)3。
The preparation method of the composite anode material of the lithium ion battery comprises the following steps:
s1, coating LiCoO 1mol with lithium acetate 0.0035mol, nickel acetate 0.0020mol, cobalt acetate 0.0005mol and manganese acetate 0.0075mol by spray drying2(97.87g) to obtain a first complex; then calcining the first compound at 800 ℃ for 5h in an air atmosphere to obtain the Li of the lithium-poor interlayer0.7Ni0.4Co0.1Mn1.5O4A positive electrode material coating material for coating lithium cobaltate;
s2, adding 2g of carbon nano tube, 0.03mol of phosphoric acid, 0.01mol of lithium hydroxide and 0.02mol of Zr (OH)4 into 300ml of ethanol, uniformly dispersing, then adding 1mol of the positive electrode material coating obtained in the step S1, and obtaining a second compound by an evaporation solvent method; calcining the second compound at 1000 ℃ for 0.5h in a nitrogen atmosphere to obtain the Li of the lithium-poor interlayer0.7Ni0.4Co0.1Mn1.5O4Carbon nanotube as electron conductor and LiZr as ion conductor2(PO4)3Composite coated LiCoO2Composite positive electrode material (modified sample).
Wherein the mass fraction of the lithium-poor intermediate layer in the composite cathode material is about 0.856%, the mass fraction of the composite coating layer in the composite cathode material is about 6.41%, and the mass fraction of the electron conductor in the composite coating layer is about 29.54%.
Example 4:
a composite anode material of a lithium ion battery comprises an anode base material, and a poor lithium intermediate layer and a composite coating layer which are sequentially coated on the surface of the anode base material. Wherein the positive electrode base material is LiNi with a median particle diameter of about 5 μm0.5Co0.2Mn0.3O2(i.e., as a pre-modified sample); the lithium-poor interlayer is Li0.7Ni0.4Co0.1Mn1.5O4The electronic conductor in the composite coating layer is a carbon nano tube, and the ion conductor in the composite coating layer is Li3PO4。
The preparation method of the composite anode material of the lithium ion battery comprises the following steps:
s1, coating 1mol of LiNi with 0.0035mol of lithium carbonate, 0.0040mol of nickel oxalate, 0.0010mol of cobalt oxalate and 0.0150mol of manganese oxalate by evaporating the solvent0.5Co0.2Mn0.3O2(96.55g) to obtain a first complex; then calcining the first compound for 6 hours at 700 ℃ in an air atmosphere to obtain the Li of the lithium-poor interlayer0.7Ni0.4Co0.1Mn1.5O4Coated LiNi0.5Co0.2Mn0.3O2The positive electrode material coating of (1);
s2, firstly, 1g of carbon nanotubes and 16g of Li3PO4Adding the mixture into 100ml of ethanol, uniformly dispersing, then adding 1mol of the positive electrode material coating obtained in the step S1, and carrying out spray drying to obtain a second compound; calcining the second compound for 4 hours at 600 ℃ in a nitrogen atmosphere to obtain the Li of the lithium-poor interlayer0.7Ni0.4Co0.1Mn1.5O4Electron conductor carbon nanotube and ion conductor Li3PO4Composite coated LiNi0.5Co0.2Mn0.3O2Composite positive electrode material (modified sample).
The mass fraction of the lithium-poor intermediate layer in the composite cathode material is about 1.556%, the mass fraction of the composite coating layer in the composite cathode material is about 14.62%, and the mass fraction of the electronic conductor in the composite coating layer is about 5.88%.
Example 5:
a composite anode material of a lithium ion battery comprises an anode base material, and a poor lithium intermediate layer and a composite coating layer which are sequentially coated on the surface of the anode base material. Wherein the positive electrode base material is LiCoO having a median particle diameter of about 10 μm2(i.e., as a pre-modified sample); the lithium-poor interlayer is Li0.5Co0.5Mn1.5O4The electronic conductor in the composite coating layer is amorphous carbon, and the ionic conductor is LiZr2(PO4)3。
The preparation method of the composite anode material of the lithium ion battery comprises the following steps:
s1, coating 1mol of LiCoO with 0.0005mol of lithium hydroxide, 0.0005mol of cobalt acetate and 0.0015mol of manganese acetate by using hydrothermal method2(97.87g) to obtain a first complex; then calcining the first compound for 20 hours at 450 ℃ in an air atmosphere to obtain the Li of the lithium-poor interlayer0.5Co0.5Mn1.5O4A positive electrode material coating material for coating lithium cobaltate;
s2, first, 5g of PEG and 0.5gLi3PO4Adding 100mL of ethanol, dispersing uniformly, and preparing to obtain an electronic conductor (amorphous carbon) and an ion conductor (Li) by using a solvothermal method3PO4) Then adding the composite material into 100mL of ethanol for uniform dispersion to obtain a composite material dispersion liquid; then adding 1mol of the positive electrode material coating obtained in the step S1 and obtaining a second compound by an evaporation solvent method; calcining the second compound at 400 ℃ for 6h in a nitrogen atmosphere to obtain the Li of the lithium-poor interlayer0.5Co0.5Mn1.5O4Amorphous carbon as electron conductor and Li as ion conductor3PO4Composite coated LiCoO2Composite positive electrode material (modified sample).
The mass fraction of the lithium-poor intermediate layer in the composite cathode material is about 0.148%, the mass fraction of the composite coating layer in the composite cathode material is about 1.05%, and the mass fraction of the electron conductor in the composite coating layer is about 66.66%.
Examples 6 to 8:
examples 6-8 differ from example 1 in that: examples 6 to 8 were carried out in the same manner as in example 1 except that 0.5g of carbon nanotube, 3g of conductive carbon black and 5g of polypyrrole were used instead of the electron conductor graphene oxide.
Example 9:
example 9 differs from example 4 in that: 0.0035mol of lithium carbonate, 0.0040mol of nickel oxalate, 0.0010mol of cobalt oxalate were replaced with 0.040mol of lithium acetate, 0.020mol of nickel acetate, 0.005mol of cobalt acetate, and 0.075mol of manganese acetate, and the sintering schedule of the first composite was changed to calcination at 800 ℃ for 4 hours in an oxygen atmosphere, otherwise the same as in example 4.
Example 10:
example 10 differs from example 2 in that: the same procedure as in example 2 was repeated except that 0.01mol of phosphoric acid and 0.03mol of lithium hydroxide in the step S2 were replaced with 0.06mol of phosphoric acid, 0.04mol of lithium hydroxide, 0.01mol of alumina and 0.02mol of titanium dioxide, respectively.
Examples 11 to 13:
examples 11-13 differ from example 1 in that: the preparation method in step S1 was replaced with the evaporation solvent method, the spray drying method, and the sol-gel method, respectively, and the other steps were the same as in example 1.
Examples 14 to 16:
examples 14-16 differ from example 5 in that: the matrix materials are respectively replaced by equivalent LiFePO with the median diameter of 1.0 mu m4LiFe having a median particle diameter of 0.8 μm0.2Mn0.8PO40.5Li having a median particle diameter of 4.5 μm2MnO3·0.5LiNi0.5Mn0.5O2。
Comparative example 1:
a composite anode material of a lithium ion battery comprises an anode base material and a composite coating layer coated on the surface of the anode base material. Wherein the positive electrode base material is LiCoO with a median particle diameter of about 12 μm2(i.e. isSample before modification); the electronic conductor in the composite coating layer is graphene, and the ion conductor is Li3PO4。
The preparation method comprises the following steps: 1g of graphene oxide, 0.01mol of phosphoric acid and 0.03mol of lithium hydroxide were added to 100mL of water and uniformly dispersed, and then 1mol of LiCoO was added2And obtaining a compound by an evaporation solvent method; calcining the compound for 2 hours at 500 ℃ in a nitrogen atmosphere to obtain the electronic conductor graphene and the ion conductor Li3PO4Composite coated LiCoO2And (3) compounding the positive electrode material (namely the improved sample).
Wherein the mass fraction of the composite coating layer in the composite cathode material is about 2.16%, and the mass fraction of the electronic conductor in the composite coating layer is about 46.35%.
Comparative example 2:
a composite anode material of a lithium ion battery comprises an anode base material and a composite coating layer coated on the anode base material. Wherein the positive electrode base material is LiCoO having a median particle diameter of about 10 μm2(i.e., as a pre-modified sample); the electronic conductor in the composite coating layer is a carbon nano tube, and the ionic conductor is LiZr2(PO4)3。
The preparation method comprises the following steps: 2g of carbon nanotubes, 0.03mol of phosphoric acid, 0.01mol of lithium hydroxide and 0.02mol of Zr (OH)4 are added into 300ml of ethanol to be uniformly dispersed, and then 1mol of LiCoO is added2And obtaining a compound by an evaporation solvent method; calcining the compound for 0.5h at 1000 ℃ in a nitrogen atmosphere, wherein the carbon nano tube is an electronic conductor and the LiZr is an ionic conductor2(PO4)3Composite coated LiCoO2And (3) compounding the positive electrode material (namely the improved sample). The composite coating layer accounts for about 6.47% of the composite cathode material, and the electronic conductor accounts for about 29.54% of the composite coating layer.
Comparative example 3:
comparative example 3 differs from comparative example 2 in that: the matrix material was changed to LiNi having a median particle diameter of 5 μm0.5Co0.2Mn0.3O2The rest is the same as in comparative example 2.
Comparative example 4:
comparative example 4 differs from comparative example 2 in that: 0.03mol of phosphoric acid, 0.01mol of lithium hydroxide and 0.02mol of Zr (OH)4 are replaced by 2g of LiAlO2And the sintering conditions in the step S1 were changed to 500 ℃ sintering for 14 hours, otherwise the same as in comparative example 2.
Performance comparison experiment two:
the positive electrode base material before improvement and the composite positive electrode material after improvement in examples 3 to 16 and the composite material in comparative examples 1 to 4 are respectively made into pole pieces, and are used as working electrodes to assemble a mixed solid-liquid lithium ion battery or a liquid lithium ion battery, and the battery is subjected to charge and discharge tests, except that the test voltages of examples 14 and 15 are 2.5 to 3.7V, the test voltage ranges of other cases are 2.8 to 4.5V, the first discharge specific capacity and the first coulombic efficiency are tested at 0.1C/0.1C, the rate capability is tested at 0.1C/0.1C two weeks, 0.2C/0.2C two weeks, 0.5C/0.5C two weeks, 0.5C/1C two weeks, 1C/1C two weeks, and the cycle capacity retention rate is tested at 1C/1C for 100 weeks, and the results are shown in tables 3 and 4.
Table 3 comparison of results of specific first discharge capacity, first coulombic efficiency and cycle performance of samples in examples 3 to 16
As can be seen from table 3, the first discharge capacity, the first coulombic efficiency and the 100-cycle retention rate of the mixed solid-liquid lithium ion battery prepared from the composite cathode material improved by the method of the present invention are all greatly improved compared with the cathode matrix material before the improvement.
TABLE 4 comparison of specific first discharge capacity, first coulombic efficiency and cycle performance results for samples in examples 1 and 3 and comparative examples 1 to 4
As can be seen from Table 4, although the improved samples of comparative examples 1-4 have improved performance to some extent, the improved samples of examples 1 and 3 have better electrochemical performance.
The sample preparation processes of comparative examples 1 to 4 were the same as or similar to those of examples 1 and 3, respectively, except that no lithium-deficient interlayer precursor was added. In the samples of comparative examples 1 to 4, the ion conductor and the electron conductor were coated on the surface of the substrate in addition to the absence of the intermediate layer of the spinel phase in a lithium-poor state. However, since the poor lithium intermediate layer does not exist in the preparation process, the electronic conductor material may have a certain chemical reaction with the substrate in the sintering process, which may cause a certain structural damage to the substrate, thereby affecting the cycle performance. Meanwhile, the interlayer of the lithium-poor spinel phase has a three-dimensional lithium ion transmission channel, which is beneficial to improving the electrochemical performance of the material. Therefore, the sample modified by the lithium-poor intermediate layer, the ion conductor and the electronic conductor composite coating layer has more excellent electrochemical performance than the sample only coated with the ion conductor and the electronic conductor.
The lithium-poor spinel structure intermediate layer used in the invention can improve the ionic conductivity of the surface of the anode matrix material, and has good electronic conductivity and ionic conductivity on the surface of the anode material under the action of the electronic conductor and the ion conductor coating layer, thereby well improving the coulombic efficiency and the rate capability of the composite anode material. The composite coating layer coated by the invention not only can reduce the direct contact between the anode base material and the electrolyte, but also can provide certain buffer for the volume change of the anode base material in the lithium desorption process, thereby improving the cycle performance of the material.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (15)
1. The composite cathode material of the lithium ion battery is characterized in that: the lithium ion battery comprises a positive electrode base material, and a lithium-poor intermediate layer and a composite coating layer which are sequentially coated on the surface of the positive electrode base material; the lithium-poor intermediate layer is Li with a spinel structurexMx1Mn2-x1O4Wherein 0 is less than or equal to x<2，0≤x1<2, M is one or more of Ni, V, Co, Cr, Cu, Fe, Mo, Al, La, Mg, Ca, Ge, Gd and B; the composite cladding layer comprises an electron conductor and an ion conductor.
2. The lithium ion battery composite positive electrode material according to claim 1, characterized in that: the mass fraction of the poor lithium intermediate layer in the lithium ion battery composite anode material is 0.01-15%.
3. The lithium ion battery composite positive electrode material according to claim 1, characterized in that: the positive electrode base material is at least one of lithium iron phosphate, lithium manganese phosphate, lithium iron manganese phosphate, lithium cobalt phosphate, lithium vanadium phosphate, lithium cobaltate, lithium nickelate, lithium manganate, lithium nickel cobalt manganese, lithium nickel cobalt aluminate, lithium nickel manganese and lithium-rich layered oxide.
4. The lithium ion battery composite positive electrode material according to claim 1, characterized in that: the mass fraction of the composite coating layer in the composite anode material of the lithium ion battery is 0.01-40%.
5. The lithium ion battery composite positive electrode material according to claim 1 or 4, characterized in that: the electronic conductor is one or more of amorphous carbon, conductive graphite, nano graphite, conductive carbon black, carbon nano tubes, carbon fibers, fullerene, graphene, conductive polymers or partially carbonized conductive polymers.
6. The lithium ion battery composite positive electrode material according to claim 1 or 4, characterized in that: the conductive polymer is at least one selected from polyacetylene, polythiophene, polypyrrole, polyaniline, polyphenylene ethylene or polydiyne.
7. The lithium ion battery composite positive electrode material according to claim 1 or 4, characterized in that: the ion conductor comprises Li1+aAlaGe2-a(PO4)3、Li3bLa2/3-bTiO3、LiZr2-cTic(PO4)3、Li1+yAlyTi2-y(PO4)3、Li4-zGe1-zPzS4、Li7-2n-mM’nLa3Zr2-mM”mO12、Li7P3S11、Li3PS4、Li3PO4、Li4P2O7、LiPO3、Li3BO3、Li2B4O7、Li2ZrO3、LiAlO2、LiNbO3、Li4SnS4、Li4Ti5O12、Li4SiO4、Li2SiO3、LiTaO3、Li2CO3、Li4GeO4One or more of LiF; wherein a is more than or equal to 0 and less than or equal to 2, b is more than or equal to 0 and less than or equal to 2/3, c is more than or equal to 0 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 2, z is more than or equal to 0 and less than or equal to 1, n is more than or equal to 0 and less than or equal to 3, M is more than or equal to 0 and less than or equal to 2, M 'is at least one of Ge and Al, and M' is one or more of Nb, Ta, Te and W.
8. The lithium ion battery composite positive electrode material according to claim 1, characterized in that: the median diameter D of the positive electrode base material50Not more than 30 μm; the thickness of the lithium-poor intermediate layer is not more than 500 nm; the thickness of the composite coating layer is not more than 5 mu m.
9. A preparation method of a lithium ion battery composite anode material is characterized by comprising the following steps: the method comprises the following steps:
s1, coating the lithium-poor intermediate layer precursor on the positive electrode base material to obtain a first compound; calcining the first compound at 300-1200 ℃ for 0.1-30 h to obtain a positive electrode material coating of the poor lithium intermediate layer coating positive electrode base material;
s2, dispersing the electron conductor precursor and the ion conductor precursor in a liquid reagent, adding the anode material coating prepared in the step S1, and coating the electron conductor precursor and the ion conductor precursor on the anode material coating to obtain a second compound; and calcining the second compound in an inert atmosphere at 50-1200 ℃ for 0.1-30 h to obtain the lithium ion battery composite anode material with the lithium-poor intermediate layer and the composite coating layer coating the anode base material.
10. The method for preparing the composite positive electrode material of the lithium ion battery according to claim 9, wherein: the lithium-poor intermediate layer precursor in the step S1 is LixMx1Mn2-x1O4Wherein 0 is less than or equal to x<2，0≤x1<2, M is one or more of Ni, V, Co, Cr, Cu, Fe, Mo, Al, La, Mg, Ca, Ge, Gd and B; or can synthesize LixMx1Mn2-x1O4Corresponding to M, Mn and Li.
11. The method for preparing the composite positive electrode material of the lithium ion battery according to claim 9, wherein: the electronic conductor precursor in step S2 is one or more of amorphous carbon, conductive graphite, nano-graphite, conductive carbon black, carbon nanotubes, carbon fibers, fullerenes, graphene, conductive polymers or partially carbonized conductive polymers; or a corresponding substance capable of synthesizing amorphous carbon, conductive graphite, nanographite, conductive carbon black, carbon nanotubes, carbon fibers, fullerenes, graphene, conductive polymers or partially carbonized conductive polymers.
12. The method for preparing the composite positive electrode material of the lithium ion battery according to claim 9, wherein: the ion guide in the step S2The bulk precursor is Li1+aAlaGe2-a(PO4)3、Li3bLa2/3-bTiO3、LiZr2-cTic(PO4)3、Li1+ yAlyTi2-y(PO4)3、Li4-zGe1-zPzS4、Li7-2n-mM’nLa3Zr2-mM”mO12、Li7P3S11、Li3PS4、Li3PO4、Li4P2O7、LiPO3、Li3BO3、Li2B4O7、Li2ZrO3、LiAlO2、LiNbO3、Li4SnS4、Li4Ti5O12、Li4SiO4、Li2SiO3、LiTaO3、Li2CO3、Li4GeO4And one or more of LiF, wherein a is more than or equal to 0 and less than or equal to 2, b is more than or equal to 0 and less than or equal to 2/3, c is more than or equal to 0 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 2, z is more than or equal to 0 and less than or equal to 1, n is more than or equal to 0 and less than or equal to 3, M is more than or equal to 0 and less than or equal to 2, M 'is at least one of Ge and Al, and M' is one or more of Nb, Ta, Te and W; ion conductor precursors or precursors capable of synthesizing Li1+aAlaGe2-a(PO4)3、Li3bLa2/3-bTiO3、LiZr2-cTic(PO4)3、Li1+yAlyTi2-y(PO4)3、Li4-zGe1-zPzS4、Li7-2n-mM’nLa3Zr2-mM”mO12、Li7P3S11、Li3PS4、Li3PO4、Li4P2O7、LiPO3、Li3BO3、Li2B4O7、Li2ZrO3、LiAlO2、LiNbO3、Li4SnS4、Li4Ti5O12、Li4SiO4、Li2SiO3、LiTaO3、Li2CO3、Li4GeO4Or LiF.
13. The method for preparing the composite positive electrode material of the lithium ion battery according to claim 9, wherein: the liquid reagent in step S2 is at least one of water, methanol, ethanol, propanol, isopropanol, ethylene glycol, benzyl alcohol, acetic acid, N-methylpyrrolidone, acetone, acetonitrile, tetrahydrofuran, dimethyl carbonate, propylene carbonate, benzene, toluene, xylene, methyl ether, ethyl ether, and ethylene glycol dimethyl ether.
14. The method for preparing the composite positive electrode material of the lithium ion battery according to claim 9, wherein: the inert atmosphere in the step S2 is one or more of nitrogen, argon, helium, neon, carbon monoxide and carbon dioxide.
15. The application of the lithium ion battery composite positive electrode material as defined in any one of claims 1 to 8 in the preparation of a lithium ion battery, is characterized in that: the lithium ion battery is a liquid lithium ion battery, a mixed solid-liquid metal lithium battery, an all-solid lithium ion battery or an all-solid metal lithium battery.
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