CN107170970B - A kind of optimization method of lithium electricity electrode material surface solid solution layer material - Google Patents

A kind of optimization method of lithium electricity electrode material surface solid solution layer material Download PDF

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CN107170970B
CN107170970B CN201710348650.9A CN201710348650A CN107170970B CN 107170970 B CN107170970 B CN 107170970B CN 201710348650 A CN201710348650 A CN 201710348650A CN 107170970 B CN107170970 B CN 107170970B
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block materials
lithium
materials
solid solution
block
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CN107170970A (en
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黄冰心
胡希韬
强文江
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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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
    • H01M4/36—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
    • H01M4/52—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The invention belongs to lithium electric material technical fields, especially one kind is using lithium electricity positive or negative pole material as matrix, it is according to selection solid solution ingredient with mechanics and electric conductivity, this solid solution is coated on electrode particle, cycle performance of lithium ion battery can be improved to greatly improve a kind of optimization method of lithium electricity electrode material surface of battery solid solution layer material in this surface solid solution layer.Specifically: basis material is mixed in specific proportions with dopant material, block materials are made by series of process in the mixture, test block material mechanical performance and electric conductivity, optimal ingredient is selected as covering material using mechanical property and electric conductivity as judgment basis, and optimal ingredient is coated on behind blapharoplast surface layer i.e. acquisition modified electrode basis material.The present invention is by mechanics and conducting performance test alternatively foundation, and relatively traditional trial-and-error method improves efficiency, and more has specific aim, and material prepared cycle performance has compared with protocorm material to be increased substantially.

Description

A kind of optimization method of lithium electricity electrode material surface solid solution layer material
Technical field
The present invention applies in lithium electricity electrode material field, using mechanical property and electric conductivity as selection gist, is applied to lithium The surface coating layer of electric electrode material at component selections optimization method.
Background technique
Lithium ion battery is widely used in the mobile electronic devices such as mobile phone, laptop, camera.In recent years Coming, the application field of lithium ion battery has greatly been widened in the development of electric car and energy storage device, meanwhile, to lithium-ion electric Higher requirements are also raised for the energy density and service life in pond.In lithium ion battery, electrode material accounts for about overall weight 30-40%, in addition, the cyclical stability of electrode material be also determine lithium ion battery service life one of the major reasons, because And electrode material is the most critical factor for determining battery energy density and service life.In various types of electrodes material, lithium transition gold Belong to oxide material with good during high electrode current potential, good electronics and ionic conductivity and the reversible deintercalation of lithium The advantages that structural stability, therefore, such compound are excellent lithium ion battery candidate electrode materials.
Energy density and cycle life are the important parameters for characterizing electrode material chemical property, it is interesting that they are all It is closely related with the mechanical stability of electrode material.In charge and discharge process, the lattice constant of electrode material is with lithium ion Abjection (or insertion) can change, such as LiCoO2Lattice constant variation reach 3%, it should be noted that for brittle electrode For material, strain > 0.1% is considered dangerous.And for given electrode material, energy density depends on can benefit Lithium ion score, when the abjection of excessive lithium ion, the mechanical property of material is deteriorated, it is easier to it is broken, therefore, energy Density is related to mechanical stability.Even if not overcharging generation, electrode material during charge and discharge cycles, lattice constant with The abjection or insertion generating period variation of lithium ion, thus cyclic stress is generated, under lesser stress, electrode can also be sent out Raw fracture, dusting make battery be no longer appropriate for further recycling to cause electrode particle poor contact.Therefore, electrode material Cycle life is strongly depend on mechanical stability.
Research has shown that surface modification can effectively improve the cycle performance of electrode material, this, which is commonly due to decorative layer, to mention High mechanics of surface intensity, prevents crackle from generating.But due to lacking quantitative experimental data, surface modification is all to use at present Trial-and-error method, process route such as Fig. 1, that is, solid solution layer directly is prepared in particle surface, and then assembled battery, detection electrification Learn performance.Optimization process is extremely complex, and there is cladding unevenly, and cladding composition of layer is difficult to control, and needs extensive work.Especially To mechanics-chemical property coupling of the electrode material in charge and discharge process, i.e., to caused by the development of electrode particle stress The mechanism study that crackle and particle surface modification are strengthened is less.
Summary of the invention
The present invention starts with from the mechanics and electric conductivity of electrode material surface clad, is electrode material according to finishing coat The fact that expect solid solution, designs and prepares the solid solution of electrode material, with mechanical property and electric conductivity alternatively foundation, phase Traditional trial-and-error method is greatly improved the efficiency.
Technical scheme is as follows: a kind of optimization method of lithium electricity electrode material surface solid solution layer material, this method Specifically includes the following steps:
Step 1: according to design ingredient, basis material and dopant material being distinguished according to different ratios in a certain range It is mixed；
Step 2: block materials are respectively prepared in the mixing material of different proportion；
Step 3: the mechanical property for the block materials that testing procedure 2 obtains respectively is selected not with mechanical property judgment basis Optimal component is filtered out in congruent block materials, most optimum materials are coated on electrode material surface and obtain modified electrode material Material.
Further, ratio is 4:0 ~ 4:1 in the step 1, is limited in the solid solubility of dopant material.
Further, mechanic property test method in the step 3 are as follows: block materials are placed in micrometer/nanometer indentation equipment Test platform on, the pressure of application are as follows: 0.1 ~ 10 N respectively obtains the hardness of tested block materials, fracture toughness and poplar Then tested block materials are carried out de- lithium processing by family name's modulus, when deviating from 50% lithium, be tested the Ying Du ﹑ fracture of material Toughness and Young's modulus decline in 20%, as most optimum materials.
Further, this method is further comprising the steps of, when under the Ying Du ﹑ fracture toughness and Young's modulus of two kinds of block materials It is by testing the electric conductivity of two kinds of block materials, block materials two sides is gold-plated when depreciation is all in 20%, it is hindered using exchange Anti- spectrometer and DC resistance meter measurement ionic conductance and electronic conductance, obtain the conductivity of block materials, select conductivity high Block materials are most optimum materials.
The advantage of the invention is that relatively traditional trial-and-error method is significantly in conjunction with mechanics and electrical performance testing alternatively foundation Efficiency is improved, and more there is specific aim, material prepared cycle performance has compared with protocorm material to be increased substantially.
Detailed description of the invention
Fig. 1 is the selection of conventional lithium ion battery surfacing and manufacturing process
Fig. 2 is the selection of this technique lithium ion battery surface material and manufacturing process
Fig. 3 is finishing coat effect diagram.
Fig. 4 is particle after cladding.
Fig. 5 is the matrix cycle performance.
Fig. 6 NCA-Ti20 and NCA, NCA-Ti10 (Li (Ni0.8CO0.15Al0.05)0.9Ti0.1O2) mechanical property comparison.
Specific embodiment
Technical solution of the present invention is described further combined with specific embodiments below, but this method be not limited to Lower embodiment.
A kind of optimization method of lithium electricity electrode material surface solid solution layer material of the present invention, this method specifically include following step It is rapid:
Step 1: according to design ingredient, basis material and dopant material being distinguished according to different ratios in a certain range It is mixed；
Step 2: block materials are respectively prepared in the mixing material of different proportion；
Step 3: the mechanical property for the block materials that testing procedure 2 obtains respectively is selected not with mechanical property judgment basis Optimal component is filtered out in congruent block materials, most optimum materials are coated on electrode material surface and obtain modified electrode material Material.
Further, ratio is 4:0 ~ 4:1 in the step 1, is limited in the solid solubility of dopant material.
Mechanic property test method in step 3 described further are as follows: block materials are placed in micrometer/nanometer indentation equipment On test platform, the pressure of application are as follows: 0.1 ~ 10 N respectively obtains the hardness of tested block materials, fracture toughness and Young Then tested block materials are carried out de- lithium processing by modulus, when deviating from 50% lithium, the Ying Du ﹑ fracture for being tested material is tough Property and Young's modulus decline in 20%, as most optimum materials.
This method is further comprising the steps of, when two kinds of block materials Ying Du ﹑ fracture toughness and Young's modulus drop-out value all It is by testing the electric conductivity of two kinds of block materials, block materials two sides is gold-plated when in 20%, utilize AC impedance spectrometer Ionic conductance and electronic conductance are measured with DC resistance meter, obtains the conductivity of block materials, the block material for selecting conductivity high Material is most optimum materials.
Embodiment 1:
1) by basis material (LiNi0.8CO0.15Al0.05O2) with dopant material respectively with molar ratio 9:1,4:1 ratio is mixed It closes, wherein dopant material is nanoscale TiO2With Li2CO3Its molar ratio is 1:1 ~ 1:1.1.
2) by mixture in just burning in lithium carbonate decomposition temperature to progress in temperature range under material melting point, more excellent is 650 DEG C ~ 800 DEG C at keep the temperature 6 ~ 8 hours, bring it about abundant reaction.
3) it will just burn after product crushes again and suppress, be sintered with being higher than just burning temperature, so that crystal grain be made to sufficiently grow But unsuitable excessively high to prevent abnormal grain growth, uneven so as to cause block sintering, more excellent section is 700 ~ 1000 DEG C, 8 ~ 12 hours burnings of heat preservation obtain target product NCA-Ti10, NCA-Ti20
4) mechanical property and electrical performance testing, these three mechanics of materials are carried out to NCA, NCA-Ti10, NCA-Ti20 It preferably can be NCA-Ti20 with conductivity, therefore determine that NCA-Ti20 is optimal covering material
5) NCA-Ti20 is coated on behind NCA particle surface layer and obtains modified NCA positive electrode.
Its finishing coat effect diagram such as Fig. 3.
Particle (d, e, f) and preceding particle (a, the b, c) SEM of cladding compare photo such as Fig. 4 after cladding.
The covering material cycle performance such as Fig. 5.
NCA-Ti20 and the comparison of NCA, NCA-Ti10 mechanical property are Fig. 6.

Claims (3)

1. a kind of optimization method of lithium electricity electrode material surface solid solution layer material, which is characterized in that this method specifically includes following Step:
Step 1: according to design ingredient, by the basis material containing lithium from the dopant material containing lithium in a certain range according to different Ratio is mixed respectively；
Step 2: block materials are respectively prepared in the mixing material of the mixed different proportion of step 1；
Step 3: the mechanical property for the block materials that testing procedure 2 obtains respectively, with mechanical property judgment basis select it is different at Most optimum materials are coated on electrode material surface and obtain modified electrode material by the component that most optimum materials are filtered out in the block materials divided Material；
Mechanic property test method in the step 3 are as follows: block materials are placed in the test platform of micrometer/nanometer indentation equipment On, the pressure of application are as follows: 0.1 ~ 10 N respectively obtains the hardness of tested block materials, fracture toughness and Young's modulus, then Tested block materials are subjected to de- lithium processing and are tested the Ying Du ﹑ fracture toughness and Young mould of material when deviating from 50% lithium Amount declines in 20%, as most optimum materials.
2. the method according to claim 1, wherein basis material containing lithium in the step 1 with containing lithium The molar ratio of dopant material is 4:0 ~ 4:1, is limited in the solid solubility of dopant material.
3. the method according to claim 1, wherein this method is further comprising the steps of, when two kinds of block materials Ying Du ﹑ fracture toughness and Young's modulus drop-out value all in 20% when, pass through test two kinds of block materials electric conductivity, will Block materials two sides is gold-plated, using AC impedance spectrometer and DC resistance meter measurement ionic conductance and electronic conductance, obtains block The conductivity of material, the block materials for selecting conductivity high are most optimum materials.
CN201710348650.9A 2017-05-17 2017-05-17 A kind of optimization method of lithium electricity electrode material surface solid solution layer material Expired - Fee Related CN107170970B (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103633314A (en) * 2013-10-28 2014-03-12 江苏金和源新材料有限公司 Preparation method of positive pole material, namely lithium manganese for compound modified lithium ion battery
CN105470455A (en) * 2014-09-03 2016-04-06 中国科学院宁波材料技术与工程研究所 Modified lithium ion battery positive electrode material and preparation method therefor

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103633314A (en) * 2013-10-28 2014-03-12 江苏金和源新材料有限公司 Preparation method of positive pole material, namely lithium manganese for compound modified lithium ion battery
CN105470455A (en) * 2014-09-03 2016-04-06 中国科学院宁波材料技术与工程研究所 Modified lithium ion battery positive electrode material and preparation method therefor

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Charge–discharge properties of surface-modified carbon by resin coating in Li-ion battery;J.-S.Kim，et al.;《Journal of Power Sources》;20020126;标题、第178页右栏倒数第1段-第179页左栏第1段 *

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