CN109411722A - Spinel type lithium ion battery positive electrode active material, preparation method thereof, positive electrode plate and lithium ion battery - Google Patents

Spinel type lithium ion battery positive electrode active material, preparation method thereof, positive electrode plate and lithium ion battery Download PDF

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Publication number
CN109411722A
CN109411722A CN201811199878.7A CN201811199878A CN109411722A CN 109411722 A CN109411722 A CN 109411722A CN 201811199878 A CN201811199878 A CN 201811199878A CN 109411722 A CN109411722 A CN 109411722A
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ion battery
active material
lithium ion
positive electrode
preparation
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孙巍巍
郑春满
谢凯
李宇杰
罗世强
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National University of Defense Technology
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National University of Defense Technology
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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
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • 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
    • 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
    • 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

The invention discloses a spinel type lithium ion battery positive electrode active material, a preparation method thereof, a positive electrode plate and a lithium ion battery. The anode active material is in a micro-nano hierarchical structure and is composed of hollow nano microspheres assembled by spinel type active material nano sheets, and the nano sheets take {111} crystal faces as main exposed faces. The preparation method of the positive active material comprises the following steps: growing MnO on the surface of PS microsphere by using PS microsphere as template2Nanosheets, and doping with Li by solvent evaporation+And/or Ni2+And then sintering at high temperature. The positive pole piece consists of the positive active material, superconducting carbon and PVDF according to the mass ratio of 80:10: 10. The lithium ion battery mainly comprises the positive pole piece. Compared with the existing lithium ion battery anode material, the lithium ion battery anode active material has excellent cycle performance, rate performance and excellent long-period cycle performance under high current density.

Description

A kind of spinel-type lithium-ion battery anode active material and preparation method thereof, anode Pole piece and lithium ion battery
Technical field
The present invention relates to lithium ion battery preparation technical field, especially a kind of spinel-type lithium-ion battery positive electrode active Material and preparation method thereof, and using anode pole piece and lithium ion battery made of the anode active material of lithium ion battery.
Background technique
With the sustained and rapid development in the fields such as portable electronic device and electric car, human society to answering extensively at present Lithium-ion battery system proposes more harsh requirement.Therefore, have excellent quick charge/discharge performance, it is excellent The research and development of the high performance lithium ion battery of the requirements such as longer cycle cycle performance is to promotion social development under larger current It has very important significance.
For current anode active material of lithium ion battery research, LiNi0.5Mn1.5O4Or LiMn2O4Since it is higher Operating voltage and theoretical specific capacity and quite by numerous researchers favor, be next-generation commercial li-ion battery anode active material Most promising candidate.
However current Spinel positive electrode active materials LiNi0.5Mn1.5O4Or LiMn2O4Cycle performance, especially larger electricity The main reason for cycle performance under current density is poor is the dissolution of Mn and Mn in material3+Caused Jahn-Teller distortion Structure degradation caused by effect.It makes a general survey of at present to LiNi0.5Mn1.5O4Or LiMn2O4The correlative study report of positive electrode active materials, Most of work, which is limited only to the indirect means such as the regulation of material microscopic appearance, surface cladding, improves battery performance.
Summary of the invention
The present invention provides a kind of spinel-type lithium-ion battery anode active material, for overcoming Mn dissolution in the prior art Caused cycle performance is poor, and especially the cycle performance under larger current density is poor；Quick charge/discharge performance is not good enough； The defects of high rate performance is not high enough, realize the lower Mn meltage of lithium ion battery, excellent cycle performance and high rate performance, with And excellent long period cycle performance under high current density.
To achieve the above object, the present invention proposes a kind of spinel-type lithium-ion battery anode active material, the anode Active material is spinel-type positive electrode, and the spinel-type positive electrode is in micro-nano hierarchical structure, by several hollow nanometers Microballoon composition, the hollow nanospheres are assembled by several nanometer sheets, { 111 } the crystal face exposure journey of several nanometer sheets Degree is greater than 90%, and the thickness of the nanometer sheet is between 8~12nm.
To achieve the above object, the present invention also provides a kind of preparation sides of spinel-type lithium-ion battery anode active material Method, comprising the following steps:
(1) the PS microballoon for being 180~220nm using partial size is grown using in situ synthesis in PS microsphere surface as template MnO2Nanometer sheet obtains MnO2@PS presoma；
It is the deionized water of 12:1, in concentrated nitric acid mixed solution that PS microballoon, which is dispersed in volume ratio, and ultrasound is equal to PS microballoon Even dispersion, it is 25mmol/L and KMnO that concentration is added later4:H2SO4Molar ratio be 2:1 mixed aqueous solution, be placed on constant temperature It is stirred in water-bath, clean products therefrom repeatedly with deionized water later and is collected by centrifugation, dries；
(2) by MnO2@PS presoma is dispersed in dehydrated alcohol, and CH is added3COOLi·2H2O and/or Ni (CH3COO)2· 4H2O solid powder mixes Li by solvent evaporated method+And/or Ni2+；
(3) sample obtained by step (2) is subjected to high temperature sintering, obtains anode active material of lithium ion battery.
To achieve the above object, the present invention also provides a kind of anode slice of lithium ion battery, and the anode pole piece is by quality Than positive electrode active materials, superconduction carbon, the binder PVDF composition for 80:10:10, the positive electrode active materials are above-mentioned anode Active material.
To achieve the above object, the present invention also provides a kind of lithium ion batteries, and the lithium ion battery is mainly by positive pole Piece, electrolyte, diaphragm and cathode pole piece composition, the anode pole piece are above-mentioned anode pole piece.
Compared with prior art, the beneficial effects of the present invention are as follows:
1. anode active material of lithium ion battery of the invention is in micro-nano hierarchical structure, compared to being reported at present by primary micro- The solid construction that assembles of grain, the graded porous structure are more advantageous to electrolyte infiltration, thus guarantee during discharge compared with High active material utilization.
2. anode active material of lithium ion battery of the invention is spinel-type positive electrode, the spinel-type anode material Material is made of several hollow nanospheres, and the hollow nanospheres are assembled by several nanometer sheets, several nanometer sheets { 111 } crystal face degree of exposure be greater than 90%, Spinel LiNi0.5Mn1.5O4Or LiMn2O4{ 111 } of positive electrode active materials are brilliant Face has higher Mn dissociation energy with respect to { 110 } crystal face and { 100 } crystal face, shows that the dissolution of the Mn on { 111 } crystal face is more tired Therefore difficulty uses LiNi made from preparation method of the present invention0.5Mn1.5O4Or LiMn2O4Lithium ion cell positive activity material Material can utmostly limit the dissolution and Jahn-Teller twisted effect of Mn from the root, to guarantee that excellent battery follows Ring performance and quick charge/discharge performance.In addition, the transmission range of lithium ion can be effectively reduced in the structure, increase electrode The contact area of material and electrolyte, to improve the high rate performance of lithium ion battery.
3. the present invention provides a kind of lithium ion battery, using anode pole piece of the present invention, the anode pole piece is used Anode active material of lithium ion battery of the invention, compared to the lithium relatively reported in the literature at present for preparing or being modified using other methods Ion battery, lithium ion battery of the present invention have more excellent cycle performance and high rate performance and excellent quick Charge/discharge performance has apparent breakthrough in comprehensive electrochemical.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with The structure shown according to these attached drawings obtains other attached drawings.
Fig. 1 a is MnO in embodiment 1 and embodiment 22The SEM of@PS presoma schemes；
Fig. 1 b is MnO in embodiment 1 and embodiment 22The TEM of@PS presoma schemes；
Fig. 1 c is LiNi in embodiment 10.5Mn1.5O4SEM figure；
Fig. 1 d is LiNi in embodiment 10.5Mn1.5O4TEM figure；
Fig. 1 e is LiMn in embodiment 22O4SEM figure；
Fig. 1 f is LiMn in embodiment 22O4TEM figure；
Fig. 2 a is MnO in comparative example 12SEM figure；
Fig. 2 b is LiNi in comparative example 10.5Mn1.5O4SEM figure；
Fig. 2 c is LiMn in comparative example 22O4SEM figure；
Fig. 3 a is LiNi in embodiment 10.5Mn1.5O4HRTEM figure；
Fig. 3 b is LiMn in embodiment 22O4HRTEM figure；
Fig. 4 a is LiNi in embodiment 10.5Mn1.5O4XRD spectrum；
Fig. 4 b is LiMn in embodiment 22O4XRD spectrum；
Fig. 5 a is the cycle performance curve of lithium ion battery described in embodiment 3 and comparative example 3；
Fig. 5 b is the cycle performance curve of lithium ion battery described in embodiment 4 and comparative example 4；
Fig. 5 c is the high rate performance curve of lithium ion battery described in embodiment 3 and comparative example 3；
Fig. 5 d is the high rate performance curve of lithium ion battery described in embodiment 4 and comparative example 4；
Fig. 6 a is the long period cycle performance curve under the high current density of lithium ion battery described in embodiment 3；
Fig. 6 b is the long period cycle performance curve under the high current density of lithium ion battery described in embodiment 4.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete Site preparation description, it is clear that the described embodiments are merely a part of the embodiments of the present invention, instead of all the embodiments.It is based on Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other Embodiment shall fall within the protection scope of the present invention.
Embodiment 1
In the present embodiment, the positive electrode active materials are in micro-nano hierarchical structure, are made of several hollow nanospheres；
The characterization result of positive electrode active materials described in the present embodiment is as shown in Fig. 3 a, Fig. 4 a.
The present embodiment provides a kind of spinel-type lithium-ion battery anode active material LiNi0.5Mn1.5O4Preparation method, The following steps are included:
(1) the PS microballoon for being 180~220nm using partial size is grown using in situ synthesis in PS microsphere surface as template MnO2Nanometer sheet obtains MnO2@PS presoma, pattern are as shown in Figure 1 a, 1 b；
Taking 0.1g PS microballoon to be dispersed in 65mL volume ratio is the deionized water of 12:1, in concentrated nitric acid mixed solution, and ultrasound is extremely PS microballoon is evenly dispersed, and it is 25mmol/L and KMnO that concentration is added later4:H2SO4Molar ratio is the mixed aqueous solution of 2:1 (KMnO4:3mmol、H2SO4: 1.5mmol), be placed in thermostat water bath the 2000r/min magnetic agitation 3h at 75 DEG C, it It cleans products therefrom repeatedly with deionized water afterwards and is collected by centrifugation, in a vacuum drying oven 60 DEG C of dry 12h；
(2) by MnO2@PS presoma is dispersed in 60mL dehydrated alcohol, and 2mmol CH is added3COOLi·2H2O and 1mmol Ni(CH3COO)2·4H2O solid powder, by mixed solution be placed at room temperature 2000r/min magnetic agitation to solvent absolute ethyl alcohol It is evaporated, finally collects gained powder sample；
(3) high temperature sintering recrystallization preparation LiNi0.5Mn1.5O4.Powder sample obtained by step (2) is placed in ceramic earthenware It is placed in Muffle furnace center in crucible, be warming up to 450 DEG C first in air atmosphere with the heating rate of 2 DEG C/min and keeps the temperature Then 3h is warming up to 700 DEG C with the heating rate of 5 DEG C/min and keeps the temperature 6h, after naturally cool to collecting product after room temperature, the production Object is LiNi described in the present embodiment0.5Mn1.5O4Anode active material of lithium ion battery, pattern is as shown in Fig. 1 c, Fig. 1 d.
Embodiment 2
In the present embodiment, the positive electrode active materials are in micro-nano hierarchical structure, are made of several hollow nanospheres；
This implements the characterization result of the positive electrode active materials as shown in Fig. 3 b, Fig. 4 b.
The present embodiment provides a kind of spinel-type lithium-ion battery anode active material LiMn2O4Preparation method, including with Lower step:
(1) the PS microballoon for being 180~220nm using partial size is grown using in situ synthesis in PS microsphere surface as template MnO2Nanometer sheet obtains MnO2@PS presoma；With (1) the step of embodiment 1.
(2) by MnO2@PS presoma is dispersed in 60ml dehydrated alcohol, and 1.5mmol CH is added3COOLi·2H2O solid Mixed solution is placed in 2000r/min magnetic agitation to solvent absolute ethyl alcohol at room temperature and is evaporated by powder, finally collects gained powder Sample.
(3) high temperature sintering recrystallization preparation LiMn2O4.With (3) the step of embodiment 1, pattern is as shown in Fig. 1 e, Fig. 1 f.
Comparative example 1
In this comparative example, the pattern of the anode active material of lithium ion battery is solid random particle；
This comparative example provides a kind of anode active material of lithium ion battery LiNi0.5Mn1.5O4Preparation method, including it is following Step:
(1)MnO2Nanometer sheet precursor preparation；
Taking 65mL volume ratio is the deionized water of 12:1, concentrated nitric acid mixed solution, be added immediately concentration be 25mmol/L and KMnO4:H2SO4Molar ratio is the mixed aqueous solution (KMnO of 2:14:3mmol、H2SO4: 1.5mmol), then mixed solution is set In thermostat water bath at 75 DEG C 2000r/min magnetic agitation 3h.Finally, cleaned repeatedly with deionized water products therefrom and from The heart is collected, in a vacuum drying oven 60 DEG C of dry 12h, obtains MnO2Nanometer sheet presoma, pattern are as shown in Figure 2 a；
(2) by MnO2Presoma is dispersed in 60ml dehydrated alcohol, and 2mmol CH is added3COOLi·2H2O and 1mmol Ni (CH3COO)2·4H2Mixed solution is placed in 2000r/min magnetic agitation to solvent absolute ethyl alcohol at room temperature and steamed by O solid powder It is dry, finally collect gained powder sample；
(3) high temperature sintering recrystallization preparation LiNi0.5Mn1.5O4.Powder sample obtained by step (2) is placed in ceramic earthenware It is placed in Muffle furnace center in crucible, be warming up to 450 DEG C first in air atmosphere with the heating rate of 2 DEG C/min and keeps the temperature Then 3h is warming up to 700 DEG C with the heating rate of 5 DEG C/min and keeps the temperature 6h, after naturally cool to collecting product after room temperature, the production Object is LiNi described in this comparative example0.5Mn1.5O4Anode active material of lithium ion battery, pattern are as shown in Figure 2 b.
Comparative example 2
In this comparative example, anode active material of lithium ion battery LiMn2O4Pattern be solid random particle；
This comparative example provides a kind of anode active material of lithium ion battery LiMn2O4Preparation method, comprising the following steps:
(1)MnO2Nanometer sheet precursor preparation.With (1) the step of comparative example 1.
(2) by MnO2Presoma is dispersed in 60ml dehydrated alcohol, and 1.5mmol CH is added3COOLi·2H2O solid powder Mixed solution is placed in 2000r/min magnetic agitation to solvent absolute ethyl alcohol at room temperature and is evaporated by end, finally collects gained powder-like Product.
(3) high temperature sintering recrystallization preparation LiMn2O4.With (3) the step of comparative example 1, pattern is as shown in Figure 2 c.
Embodiment 3
A kind of lithium ion battery, the anode active material of lithium ion battery is using LiNi described in embodiment 10.5Mn1.5O4。
Lithium ion battery characterization result described in the present embodiment is as shown in Fig. 5 a, Fig. 5 c, Fig. 6 a.
The present embodiment provides a kind of preparation method of lithium ion battery, comprising the following steps:
(1) prepared by anode pole piece.It is in mass ratio the LiNi of 80:10:100.5Mn1.5O4, superconduction carbon, binder PVDF claim It takes above-mentioned powder sample to be placed in high-energy ball milling tank, is weighed in mass ratio for PVDF, NMP of 1:40 (N-methyl pyrrolidones) NMP is added in high-energy ball milling tank, with 400rpm revolving speed ball milling 1h, finally gained slurry is evenly applied on aluminium foil, face is close Degree control is average 1.65mg/cm2, gained pole piece is placed in a vacuum drying oven, 100 DEG C of dry 12h, after naturally cool to room The disk that diameter is 15mm is cut into after temperature.
(2) battery assembles.Lithium ion battery assembling process described in the present embodiment is completed in high-purity argon gas glove box, hand Moisture content is lower than 1ppm lower than 1ppm, oxygen content in casing.Using disk made from step (1) as anode pole piece, it is with diameter The Celgard 2400 of 19mm is diaphragm, with volume ratio for 3:7 and LiPF containing 1.2mol/L6EC/DEC (ethylene carbonate/ Diethyl carbonate) be electrolyte, using diameter for 15mm metal lithium sheet as cathode pole piece, be assembled into 2016 button cells, press Pressure is 1000psi.
Embodiment 4
A kind of lithium ion battery, the anode active material of lithium ion battery is using LiMn described in embodiment 22O4。
Lithium ion battery characterization result described in the present embodiment is as shown in Fig. 5 b, Fig. 5 d, Fig. 6 b.
The present embodiment provides a kind of preparation method of lithium ion battery, comprising the following steps:
(1) prepared by anode pole piece.It is in mass ratio the LiMn of 80:10:102O4, superconduction carbon, binder PVDF weigh it is above-mentioned Powder sample is placed in high-energy ball milling tank, is weighed NMP in mass ratio for PVDF, NMP of 1:40 and is added in high-energy ball milling tank, With 400rpm revolving speed ball milling 1h, finally gained slurry is evenly applied on aluminium foil, surface density control is average 1.65mg/cm2, Gained pole piece is placed in a vacuum drying oven, 100 DEG C of dry 12h, after naturally cool to be cut into after room temperature diameter be 15mm circle Piece.
(2) battery assembles.With (2) the step of embodiment 3.
Comparative example 3
A kind of lithium ion battery, the anode active material of lithium ion battery is using LiNi described in comparative example 10.5Mn1.5O4。
Lithium ion battery characterization result is as shown in Fig. 5 a, Fig. 5 c described in the present embodiment.
The present embodiment provides a kind of preparation method of lithium ion battery, comprising the following steps:
(1) prepared by anode pole piece.It is in mass ratio the LiNi of 80:10:100.5Mn1.5O4, superconduction carbon, binder PVDF claim It takes above-mentioned powder sample to be placed in high-energy ball milling tank, weighs NMP in mass ratio for PVDF, NMP of 1:40 and be added to high energy ball In grinding jar, with 400rpm revolving speed ball milling 1h, finally gained slurry is evenly applied on aluminium foil, surface density control is average 1.65mg/cm2, gained pole piece is placed in a vacuum drying oven, 100 DEG C of dry 12h, after naturally cool to being cut into diameter after room temperature For the disk of 15mm.
(2) battery assembles.With (2) the step of embodiment 3.
Comparative example 4
A kind of lithium ion battery, the anode active material of lithium ion battery is using LiMn described in comparative example 22O4。
Lithium ion battery characterization result is as shown in Fig. 5 b, Fig. 5 d described in the present embodiment.
The present embodiment provides a kind of preparation method of lithium ion battery, comprising the following steps:
(1) prepared by anode pole piece.It is in mass ratio the LiMn of 80:10:102O4, superconduction carbon, binder PVDF weigh it is above-mentioned Powder sample is placed in high-energy ball milling tank, is weighed NMP in mass ratio for PVDF, NMP of 1:40 and is added in high-energy ball milling tank, With 400rpm revolving speed ball milling 1h, finally gained slurry is evenly applied on aluminium foil, surface density control is average 1.65mg/cm2, Gained pole piece is placed in a vacuum drying oven, 100 DEG C of dry 12h, after naturally cool to be cut into after room temperature diameter be 15mm circle Piece.
(2) battery assembles.With (2) the step of embodiment 3.
By anode active material of lithium ion battery LiNi described in Examples 1 and 2, comparative example 1 and 20.5Mn1.5O4Or LiMn2O4It is characterized as follows:
(1) X-ray diffraction (XRD).Utilize the diffraction phenomena of X-ray in the material, the crystalline state of analysis of material, crystal Structure, crystal size, crystallised component etc..The present invention is accordingly to anode active material of lithium ion battery LiNi0.5Mn1.5O4Or LiMn2O4Carry out qualitative analysis.Test equipment: RIGAKU TTR-3X x ray diffractometer x；Test condition: radiation source is Cu targetScanning range: 2 θ=10~80 °；Scanning speed: 6 °/min.
(2) x-ray photoelectron spectroscopy (XPS).The present invention is accordingly to anode active material of lithium ion battery LiNi0.5Mn1.5O4Or LiMn2O4Surface composition and element valence carry out qualitative analysis.Test equipment: PHI-1600 type electronics Energy disperse spectroscopy.
(3) scanning electron microscope (SEM).Present invention observation of use instrument anode active material of lithium ion battery accordingly LiNi0.5Mn1.5O4Or LiMn2O4Surface appearance feature.Test equipment: Hitachi S-4800 type Flied emission scanning electron is aobvious Micro mirror.
(4) transmission electron microscope (TEM), high-resolution transmission electron microscope (HRTEM).Present invention observation of use instrument lithium accordingly Ion battery positive electrode active materials LiNi0.5Mn1.5O4Or LiMn2O4The information such as inner structural features, high-resolution lattice image, To extrapolate microstructure, the phase composition of sample.Test equipment: Tecnai F30 type transmission electron microscope.
Lithium ion battery described in embodiment 3 and 4, comparative example 3 and 4 is characterized as follows:
(1) cyclic voltammetry (CV).Test equipment: Princeton Versa STAT electrochemical workstation；Scanning speed Rate: 0.05mV/s；Voltage window: 3.5-5.0V.
(2) constant current charge/discharge is tested.Test equipment: LADNCT2001A type multichannel charging-discharge tester system；Test Voltage range: 3.5-4.9V.
(3) ac impedance measurement.Test equipment: Princeton Versa STAT electrochemical workstation；Frequency range: 0.1~1M Hz.
The above test characterizing method is the standard testing characterizing method of lithium ion battery preparation technical field, is related to It is chosen according to this field normal operation entails when undocumented parameter.
By Fig. 1 a, Fig. 1 b it is found that MnO2@PS presoma pattern is uniform, and average diameter is about 500nm, surface MnO2Nanometer Piece；By Fig. 1 c, Fig. 1 d, Fig. 1 f, Fig. 1 e it is found that being converted into LiNi through high temperature sintering recrystallization process0.5Mn1.5O4Or LiMn2O4It Afterwards, the microscopic appearance of presoma is retained, and template PS microballoon aoxidizes disappearance at high temperature, ultimately form by nanometer sheet assembling and At hollow nanospheres structure.
By Fig. 2 a, Fig. 2 b, Fig. 2 c it is found that can still generate MnO in the case where no PS microballoon does template2Nanometer Piece, still, after high temperature sintering recrystallization process, gained LiNi0.5Mn1.5O4And LiMn2O4It is unable to maintain that presoma piece Shape structure, but it is changed into irregular solid nanoparticles.Illustrate that the maintenance of laminated structure is played in the introducing of PS microsphere template Key effect.
By Fig. 3 a, 3b it is found that LiNi0.5Mn1.5O4And LiMn2O4There is { 111 } exposure, and { 111 } exposure ratio is high.
By Fig. 4 a, Fig. 4 b it is found that the positive electrode being prepared has spinel structure, and peak position and XRD standard card Matching is good, and knows { 111 } exposure ratio height.
By Fig. 5 a, Fig. 5 b, Fig. 5 c, Fig. 5 d it is found that the hollow nanospheres shape structure that nanometer sheet assembles LiNi0.5Mn1.5O4And LiMn2O4With excellent cycle performance and high rate performance, crystal face regulation and structure design are further illustrated Key effect to lithium ion battery comprehensive electrochemical.
As Fig. 6 a, Fig. 6 b it is found that using LiNi made from the method for the invention0.5Mn1.5O4And LiMn2O4Have excellent Quick charge/discharge performance.
The anode active material of lithium ion battery LiNi prepared in the present invention using PS microballoon for template0.5Mn1.5O4With LiMn2O4It is the hollow nanospheres that nanometer sheet assembles with similar microscopic appearance structure, with material in comparative example Comparison it is found that PS microsphere template play the role of in terms of laminated structure formation it is very important.With lithium-ion electric of the invention The lithium ion battery charge/discharge capacity that pond positive electrode active materials assemble is obviously improved, and cycle performance and high rate performance are obvious Improve, and can support quick charge/discharge.
The above description is only a preferred embodiment of the present invention, is not intended to limit the scope of the invention, all at this Under the inventive concept of invention, using equivalent structure transformation made by description of the invention and accompanying drawing content, or directly/use indirectly It is included in other related technical areas in scope of patent protection of the invention.

Claims (8)

1. a kind of spinel-type lithium-ion battery anode active material, which is characterized in that the positive electrode active materials are spinelle Type positive electrode, the spinel-type positive electrode are in micro-nano hierarchical structure, are made of several hollow nanospheres, described hollow Nanosphere is assembled by several nanometer sheets, and { 111 } crystal face degree of exposure of several nanometer sheets is described to receive greater than 90% The thickness of rice piece is between 8~12nm.
2. a kind of spinel-type lithium-ion battery anode active material as described in claim 1, which is characterized in that the point is brilliant Stone-type positive electrode is LiNi0.5Mn1.5O4Or LiMn2O4。
3. a kind of preparation method of spinel-type lithium-ion battery anode active material, comprising the following steps:
(1) the PS microballoon for being 180~220nm using partial size grows MnO in PS microsphere surface using in situ synthesis as template2Nanometer Piece obtains MnO2@PS presoma；
(2) by MnO2@PS presoma is dispersed in dehydrated alcohol, and CH is added3COOLi·2H2O and/or Ni (CH3COO)2·4H2O Solid powder mixes Li by solvent evaporated method+And/or Ni2+；
(3) sample obtained by step (2) is subjected to high temperature sintering, obtains anode active material of lithium ion battery.
4. a kind of preparation method of spinel-type lithium-ion battery anode active material as claimed in claim 3, feature exist In the step (1) includes:
(11) PS microballoon is dispersed in volume ratio is the deionized water of 12:1, in concentrated nitric acid mixed solution, and ultrasound is equal to PS microballoon Even dispersion；
(12) KMnO that molar ratio is 2:1 is added4、H2SO4Mixed aqueous solution, the mixed aqueous solution concentration are 25mmol/L；
(13) it is placed in 75 DEG C of thermostat water baths and stirs 3h, speed of agitator 2000r/min is cleaned with deionized water repeatedly later Products therefrom is simultaneously collected by centrifugation and dry 13h at a temperature of 60 DEG C in a vacuum drying oven.
5. a kind of preparation method of spinel-type lithium-ion battery anode active material as claimed in claim 3, feature exist In in the step (2), the solvent evaporated method is that magnetic agitation to solvent absolute ethyl alcohol is evaporated at room temperature, and revolving speed is 2000r/min。
6. a kind of preparation method of spinel-type lithium-ion battery anode active material as claimed in claim 3, feature exist In in the step (3), the atmosphere of the high-temperature sintering process is air, and the high-temperature sintering process includes:
(31) with the heating rate of 2 DEG C/min, by sintering temperature from room temperature to 450 DEG C, it is sintered 3h；
(32) with the heating rate of 5 DEG C/min, sintering temperature is warming up to 700 DEG C from 450 DEG C, is sintered 6h.
7. a kind of anode slice of lithium ion battery, which is characterized in that the anode that the anode pole piece is 80:10:10 by mass ratio Active material, superconduction carbon, binder PVDF composition, the positive electrode active materials are the described in any item anodes of claim 1~6 Active material.
8. a kind of lithium ion battery, which is characterized in that the lithium ion battery mainly by anode pole piece, electrolyte, diaphragm and is born Pole pole piece composition, the anode pole piece are anode pole piece as claimed in claim 7.
CN201811199878.7A 2018-10-16 2018-10-16 Spinel type lithium ion battery positive electrode active material, preparation method thereof, positive electrode plate and lithium ion battery Pending CN109411722A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112047381A (en) * 2019-06-05 2020-12-08 中国科学院大连化学物理研究所 Cathode with crystal face preferentially exposed for solid oxide fuel cell and preparation method and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102593456A (en) * 2011-01-12 2012-07-18 三星Sdi株式会社 Cathode active material, method preparing same, cathode and lithium battery
CN103730655A (en) * 2014-01-21 2014-04-16 中国计量学院 Preparation method of LiMn2O4-graphene composite positive electrode material
CN103762342A (en) * 2004-09-03 2014-04-30 芝加哥大学阿尔贡有限责任公司 Manganese oxide composite electrodes for lithium batteries
CN104953109A (en) * 2015-05-11 2015-09-30 中信国安盟固利电源技术有限公司 Core-shell-structure lithium manganate capable of improving high temperature resistance performance, and synthesis method of core-shell-structure lithium manganate
CN105958042A (en) * 2016-07-19 2016-09-21 哈尔滨工业大学 In-situ synthesis Li2MnO3 coated and modified lithium ion battery cathode material and synthesis method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103762342A (en) * 2004-09-03 2014-04-30 芝加哥大学阿尔贡有限责任公司 Manganese oxide composite electrodes for lithium batteries
CN102593456A (en) * 2011-01-12 2012-07-18 三星Sdi株式会社 Cathode active material, method preparing same, cathode and lithium battery
CN103730655A (en) * 2014-01-21 2014-04-16 中国计量学院 Preparation method of LiMn2O4-graphene composite positive electrode material
CN104953109A (en) * 2015-05-11 2015-09-30 中信国安盟固利电源技术有限公司 Core-shell-structure lithium manganate capable of improving high temperature resistance performance, and synthesis method of core-shell-structure lithium manganate
CN105958042A (en) * 2016-07-19 2016-09-21 哈尔滨工业大学 In-situ synthesis Li2MnO3 coated and modified lithium ion battery cathode material and synthesis method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
WEIWEI SUN，FENG CAO等: "Nanoporous LiMn2O4 nanosheets with exposed {111} facets as cathodes for highly reversible lithium-ion batteries", 《JOURNAL OF MATERIALS CHEMISTRY》 *
WEIWEI SUN，HUIQIN LIU等: "Hierarchical donut-shaped LiMn2O4 as an advanced cathode material for lithium-ion batteries with excellent rate capability and long cycle life", 《JOURNAL OF MATERIALS CHEMISTRY A》 *
XIAOLONG ZHANG, FANGYI CHENG等: "LiNi0.5Mn1.5O4 Porous Nanorods as High-Rate and Long-Life Cathodes for Li-Ion Batteries", 《NANO LETTERS》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112047381A (en) * 2019-06-05 2020-12-08 中国科学院大连化学物理研究所 Cathode with crystal face preferentially exposed for solid oxide fuel cell and preparation method and application thereof
CN112047381B (en) * 2019-06-05 2021-09-24 中国科学院大连化学物理研究所 Cathode with crystal face preferentially exposed for solid oxide fuel cell and preparation method and application thereof

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Application publication date: 20190301