CN1332459C - Lithium secondary cell composite electrode material capable of high power discharging and charging and preparing method - Google Patents
Lithium secondary cell composite electrode material capable of high power discharging and charging and preparing method Download PDFInfo
- Publication number
- CN1332459C CN1332459C CNB2004100664899A CN200410066489A CN1332459C CN 1332459 C CN1332459 C CN 1332459C CN B2004100664899 A CNB2004100664899 A CN B2004100664899A CN 200410066489 A CN200410066489 A CN 200410066489A CN 1332459 C CN1332459 C CN 1332459C
- Authority
- CN
- China
- Prior art keywords
- electrode material
- composite electrode
- preparation
- lithium secondary
- composite material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 29
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000007772 electrode material Substances 0.000 title claims abstract description 16
- 238000007599 discharging Methods 0.000 title description 5
- 229910052709 silver Inorganic materials 0.000 claims abstract description 33
- 238000002360 preparation method Methods 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 239000011159 matrix material Substances 0.000 claims abstract description 17
- 239000004332 silver Substances 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 239000002243 precursor Substances 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 238000003786 synthesis reaction Methods 0.000 claims abstract 2
- 101710134784 Agnoprotein Proteins 0.000 claims description 22
- 230000001590 oxidative effect Effects 0.000 claims description 13
- 239000012071 phase Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 claims 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 11
- 230000015556 catabolic process Effects 0.000 abstract description 8
- 238000006731 degradation reaction Methods 0.000 abstract description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 6
- 239000006258 conductive agent Substances 0.000 abstract description 3
- 238000009831 deintercalation Methods 0.000 abstract 1
- 229910052738 indium Inorganic materials 0.000 abstract 1
- 230000002687 intercalation Effects 0.000 abstract 1
- 238000009830 intercalation Methods 0.000 abstract 1
- 239000010936 titanium Substances 0.000 description 20
- 238000010189 synthetic method Methods 0.000 description 19
- 239000002609 medium Substances 0.000 description 15
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 229910012820 LiCoO Inorganic materials 0.000 description 10
- 229910015645 LiMn Inorganic materials 0.000 description 10
- 239000008187 granular material Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 8
- 229910013872 LiPF Inorganic materials 0.000 description 7
- 101150058243 Lipf gene Proteins 0.000 description 7
- 239000002033 PVDF binder Substances 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 7
- 239000006230 acetylene black Substances 0.000 description 7
- 239000005030 aluminium foil Substances 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 239000011888 foil Substances 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- -1 polypropylene Polymers 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 238000009413 insulation Methods 0.000 description 6
- 229910013716 LiNi Inorganic materials 0.000 description 5
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 229910014411 LiNi1/2Mn1/2O2 Inorganic materials 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002611 lead compounds Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 2
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 238000009412 basement excavation Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- JWZCKIBZGMIRSW-UHFFFAOYSA-N lead lithium Chemical compound [Li].[Pb] JWZCKIBZGMIRSW-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Images
Classifications
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/624—Electric conductive fillers
-
- 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
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
本发明涉及一类可高倍率充放电的锂二次电池复合电极材料及制备方法。其特征在于它是由具有锂离子脱嵌性能的含锂氧化物与金属银单质形成的复合电极材料，其组成通式为(100-y)LimAnOx/yAg表示，式中y为复合材料Ag的重量百分数，m、n和x代表相应的摩尔数，其范围是m＝1-4，n＝1-5，x＝2-12；A为Ti、Co、Ni、Mn或它们的混合体系中一种，y范围为0.1-20wt%，Ag单质分散在晶界上，充当导电剂。本发明提供的复合电极材料的制备方法或是在基体嵌锂氧化物合成过程中同时形成第二相；或是在已制成的基体化合物的基础上通过低温分解银的前驱物形成第二相银。容量退化率比可高达29.6。
The invention relates to a kind of lithium secondary battery composite electrode material capable of high-rate charge and discharge and a preparation method thereof. It is characterized in that it is a composite electrode material formed of a lithium-containing oxide with lithium ion deintercalation properties and metallic silver. Its general formula is (100-y) Li m A n O x /yAg, where y is the weight percent of the composite material Ag, m, n and x represent the corresponding moles, and its range is m=1-4, n=1-5, x=2-12; A is Ti, Co, Ni, Mn or In one of their mixed systems, y ranges from 0.1 to 20 wt%, and Ag is dispersed on the grain boundary to act as a conductive agent. The preparation method of the composite electrode material provided by the present invention either forms the second phase at the same time during the synthesis process of the matrix lithium intercalation oxide; or forms the second phase by decomposing the silver precursor at a low temperature on the basis of the prepared matrix compound silver. The capacity degradation ratio can be as high as 29.6.
Description
Technical field
The present invention relates to a class and can be used for lithium secondary battery electrode material of high power charging-discharging and preparation method thereof, belong to field of electrochemical power source.
Background technology
Lithium rechargeable battery is since early 1990s succeeds in developing, voltage height, volume are little because it has, light weight, specific energy height, memory-less effect, pollution-free, advantage such as self discharge is little, the life-span is long, become the best battery system of present combination property, obtained development at full speed, it uses a plurality of fields that have been penetrated into civilian and Military Application, comprises mobile phone, notebook computer, video camera, digital camera etc.The high capacity lithium ion battery required at aspects such as electric automobile, space flight and energy storage is both at home and abroad also in competitively developing.Because lithium secondary battery is the existing huge commercial opportunities of compact battery especially, become the place contested by all strategists of each macrocell manufacturer of the present whole world, put into bar none in the keen competition ranks.Succeeding in developing of lithium secondary battery should at first be given the credit to the breakthrough of electrode material (carbon negative pole).Equally, its excavation that further develops and still depend on new electrode material in the application in more more important field.Especially the field of attracting attention for this whole world of electric automobile, the big current work characteristic of lithium secondary battery are that can the decision battery obtain one of key of commercial applications.The positive and negative pole material that generally uses in the lithium ion battery is respectively material with carbon element and LiCoO at present
2, negative material just under development mainly contains Li
4Ti
5O
12, positive electrode has LiMn
2O
4, LiNi
xCo
yMn
1-x-yO
2, or their modified system.Wherein, LiCoO
2Theoretical specific capacity be 274mAh/g, but actual specific capacity 150mAh/g only has only 120-140mAh/g in the application.If under powerful condition of work, its actual specific capacity is then lower, this restricted greatly its as high power battery as practical application at aspects such as electric car power supplies.Therefore the high magnification service behaviour that improves lithium ion battery electrode material becomes the problem that people pay close attention at present.Yet, the electrode material of systems such as oxide all is the electronics non-conductor usually, this also is one of basic factor of restriction battery multiplying power property, in order to improve the electron conduction of these materials, the method of the more employing of people mainly is the doping of different valency element, have also that to mix expensive platinum etc. be the second phase conductive agent, can not tackle the problem at its root usually.
Summary of the invention
But purpose of the present invention just provides combination electrode material of a class high power charging-discharging and preparation method thereof.They are to have lithium ion and take off the matrix oxide of embedding performance and being composited of the second mutually silver-colored particulate by a kind of, and this second phase silver particles can form by two kinds of methods, and the preparation of composite material just has two kinds of methods.The first forms second silver mutually simultaneously in the building-up process of matrix compounds, be called for short synthetic method.Second method is that the precursor by low-temperature decomposition silver forms the second silver-colored mutually method on the basis of the matrix compounds of having made, and is called for short decomposition method.Specifically, they are the composite materials that have the two-phase compound that the oxide that contains lithium (matrix oxide) that lithium ion takes off the embedding performance and argent simple substance forms by various, silver and matrix oxide can be to form simultaneously in the synthetic process of high temperature, also can introduce in existing matrix oxide material.This class two-phase composite material can carry out the charge and discharge cycles under the high magnification condition, makes simplely, and cost is low.
Matrix oxide involved in the present invention can be used Li
mA
nO
xExpression, wherein A represents to form the non-lithium metallic element of electrode material, and as Ti, Co, Mn, Ni etc. or their mixed system and doping vario-property system, m, n and x represent the molal quantity of respective element, and their scope is m=1-4, n=1-5, x=2-12.Basic system comprises Li
4Ti
5O
12, LiCoO
2, LiNiO
2, LiMn
2O
4And on their basis, replace the various materials that obtained by element.Related composite material can be used (100-y) Li
mA
nO
x/ yAg represents that y represents the percetage by weight of Ag in composite material, and scope is 0.1%-20%, and optimum range is 0.5-15wt%, and when Ag content was lower than 0.5wt%, the improvement of the high-rate discharge ability of composite material was limited; When Ag content surpasses 15wt%,, can obviously increase cost simultaneously to the not significant effect of the raising of performance.Preparing the employed raw material of these materials can be chemical pure or analytical reagent, also can be the various compounds that satisfy the actual instructions for use of battery.As prepare LiCoO
2/ Ag composite material can adopt Li
2CO
3And Co
3O
4Or other compounds and the AgNO of cobalt
3Or Ag
2O also can directly use LiCoO for forerunner's material
2And AgNO
3Or Ag
2O is a raw material; Preparation Li
4Ti
5O
12During/Ag combination electrode material, can also directly use Li
4Ti
5O
12With AgNO
3Or Ag
2O is a raw material, also can Li
2CO
3Or other lithium lead compound, with the TiO of rutile or Detitanium-ore-type
2Lead compound and AgNO Deng titanium
3Or Ag
2O mixes after obtain behind the high temperature solid state reaction.Preparation LiMn
2O
4During the composite material of/Ag, can Li
2CO
3And MnO
2Deng the lead compound of manganese be raw material, with AgNO
3Or Ag
2O evenly mixes after solid phase synthesis obtains.Also can adopt LiMn
2O
4The direct compound with silver of oxide carries out compound.These compounds being carried out modification and preparing it and during the composite material of Ag, can adopt the solid-phase synthesis of preparation respective compound, only need to add AgNO before this
3Mix simultaneously and get final product.In the process of preparation composite material, atmosphere there is not special requirement, as long as satisfy the formation of principal phase, be good with air or oxidizing atmosphere usually, and reducing atmosphere will be unfavorable for the formation of these compounds.But the lithium secondary cell composite electrode material of high power charging-discharging provided by the invention, concrete steps are when first kind of synthetic method prepares:
1. by (100-y) Li
mA
nO
x/ yAg general formula determines that the element of m, n, x value and A is formed, and Ag predecessor doping, prepares burden;
2. be that medium carried out ball milling 4-8 hour with absolute ethyl alcohol or water, be lower than 100 ℃ down dry, and under 800-1000 ℃ of air or oxidizing atmosphere sintering, insulation 4-20 solid phase synthesis, natural cooling and obtain the composite material of matrix oxide and silver.
Second kind of decomposition method preparation process is:
1. commercially available or synthetic Li
mA
nO
xThe otide containing lighium thing directly with the predecessor of Ag, is pressed (100-y) Li
mA
nO
x/ yAg general formula is prepared burden;
2. even mixing in alcohol or aqueous medium after the 80-100 ℃ of oven dry, is heated to 300-500 ℃ in air or oxidizing atmosphere, is incubated 2-10 hour, naturally cools to room temperature and makes.
In sum, compare with existing the whole bag of tricks, characteristics of the present invention are:
(1) Ag does not enter the lattice of basis material, thereby does not influence the stability and the key property of material self;
(2) Ag is dispersed on the crystal boundary as simple substance, all serves as conductive agent;
(3) Ag forms in the process that principal phase forms simultaneously, and preparation process is very simple, and the amount of the second phase Ag that need add is little, and cost is low;
(4) Ag can stable existence under various atmosphere as second, therefore is not subjected to the restriction of service condition.
Description of drawings
Fig. 1 (a) and (b) be respectively Li
4Ti
5O
12The 96wt%Li that matrix and synthetic method obtain
4Ti
5O
12The X-ray diffraction collection of illustrative plates of/4wt%Ag composite material only contains Li in the visible resulting composite material
4Ti
5O
12With Ag two-phase compound.Stereoscan photograph shown in Figure 2 shows that the Ag particle that bright spot partly shows is dispersed in Li mutually as second
4Ti
5O
12Intercrystalline.Fig. 3 (a) and (b) be respectively LiCoO
2Matrix and decomposition method 95wt%LiCoO
2The X-ray diffraction collection of illustrative plates of/5wt%Ag composite material, the result shows and only contains LiCoO in the resulting composite material
2With Ag two-phase compound.Stereoscan photograph shown in Figure 4 shows that the Ag particle that bright spot partly shows is dispersed in LiCoO mutually as second
2Intercrystalline.
Embodiment
As embodiments of the invention 1 is with Li
2CO
3TiO with rutile-type
2And AgNO
3After 4 hours, in 850 ℃ of air or oxidizing atmosphere, calcined 12 hours by the ball milling mixing by 1: 2: 0.35 mol ratio, naturally cool to room temperature and obtain 96wt%Li
4Ti
5O
12/ 4wt%Ag composite granule.The resulting powder of above-mentioned synthetic method is levigate, in the NMP medium, make slurry by 85: 7: 8 weight ratio with acetylene black and Kynoar (PVDF), coat on the aluminium foil and carry out drying, the film of making thus is for anodal, metallic lithium foil is a negative pole, U.S. Celgard company polypropylene screen is a barrier film, with LiPF
6-PC+DMC (1: 1) is an electrolyte, discharges and recharges test, is respectively 196.9 and 163.3mAh/g in the discharge capacity first between 2.3-0.5V under 1C and the 4C multiplying power, and the same terms is the matrix compounds Li of preparation down
4Ti
5O
12Discharge capacity first be respectively 180.6 and 150.7mAh/g, contain second mutually the 2nd discharge capacity of the composite material of silver exceed 9% and 8.4% respectively.The 10th time discharge capacity, be respectively 197.8 and 156.2mAh/g when composite material 1C and 4C, basis material then is respectively 164.2 and 117.3mAh/g, attenuation rate with respect to separately the 2nd discharge capacity is, composite material is-0.46% during 1C, be 0.32% during 4C, the decay of basis material then is respectively 4.59 and 11.8%.The cyclical stability of composite material is significantly improved under various multiplying powers especially high magnification.
Embodiment 2 is with Li
2CO
3, Detitanium-ore-type TiO
2And Ag
2O is a lead compound, Li
2CO
3, TiO
2And AgNO
3Mol ratio be 1: 2: 0.47, be that medium carried out ball milling after 4 hours with the absolute ethyl alcohol, 90 ℃ of dryings, all the other are with embodiment 1.Utilize synthetic method to obtain 90wt%Li
4Ti
5O
12/ 10wt%Ag composite granule.Under the 4C multiplying power composite material and basis material the 2nd discharge capacity be respectively 164.3 and 153.7mAh/g, then be respectively 163.1 and 120.5mAh/g for the 10th time, degenerate 0.73% and 21.6% respectively.
Embodiment 3 is with Li
2CO
3TiO with rutile-type
2And AgNO
3By 1: 2: 0.174 mol ratio, with water for after the medium ball milling mixes 6 hours, 95 ℃ of dryings, calcining is 20 hours in 900 ℃ of air or oxidizing atmosphere, naturally cools to room temperature and obtains 8wt%Li
4Ti
5O
12/ 2wt%Ag composite granule.All the other are with embodiment 1.The discharge capacity of under the composite material 4C multiplying power that above-mentioned synthetic method obtains the 2nd time and the 10th time is respectively 168.5 and 167.2mAh/g, and degradation ratio is 0.8%, and the degradation ratio of the matrix compounds correspondence that the same terms prepares down is 7.2%.
Embodiment 4 is with Li
2CO
3And Co
3O
4And AgNO
3By 1.5: 1: 0.085 mol ratios, be that calcining was 18 hours in 900 ℃ of air or oxidizing atmosphere, naturally cools to room temperature and obtains 97wt%LiCoO after medium mixed 8 hours by ball milling with water
2/ 3wt%Ag composite granule.The resulting powder of above-mentioned synthetic method is levigate, in the NMP medium, make slurry by 85: 7: 8 weight ratio with acetylene black and Kynoar (PVDF), coat on the aluminium foil and carry out drying, the film of making thus is for anodal, metallic lithium foil is a negative pole, and the Celgard polypropylene screen is a barrier film, with LiPF
6-PC+DMC (1: 1) is an electrolyte, discharges and recharges test, and the 2nd of the 3.0-4.3V voltage range the time and the 10th discharge capacity are respectively 100.2 and 99.6mAh/g under the 8C multiplying power, and the same terms is the single-phase LiCoO of preparation down
2Capacity then be respectively 98.6 and 91.5mAh/g.
Embodiment 5 is with Li
2CO
3And Co
3O
4And Ag2O is that calcining was 12 hours in 950 ℃ of air or oxidizing atmosphere, naturally cools to room temperature and obtains 95wt%LiCoO after medium mixed 6 hours by ball milling by 1.5: 1: 0.071 mol ratios with alcohol
2/ 5wt%Ag composite granule.The volume test condition is with embodiment 4.The composite material that above-mentioned synthetic method obtains the 2nd time of the 3.0-4.3V voltage range and the 10th discharge capacity under the 8C multiplying power are respectively 112.5 and 110.6mAh/g, the single-phase LiCoO that the same terms prepares down
2Capacity then be respectively 105.3 and 94.2mAh/g.
Embodiment 6 is with commercially available LiCoO
2And AgNO
3Weight ratio by 12.1: 1 mixes in distillation, 100 ℃ of dry backs are heated to 500 ℃ of insulation 2h in air or oxidizing atmosphere after, naturally cool to room temperature and obtains 95wt%LiCoO equally
2/ 5wt%Ag composite granule.The resulting powder of above-mentioned decomposition method is levigate, in the NMP medium, make slurry by 85: 7: 8 weight ratio with acetylene black and Kynoar (PVDF), coat on the aluminium foil and carry out drying, the film of making thus is for anodal, metallic lithium foil is a negative pole, and the Celgard polypropylene screen is a barrier film, with LiPF
6-PC+DMC (1: 1) is an electrolyte, discharges and recharges test, and the 2nd of the 3.0-4.3V voltage range the time and the 10th discharge capacity are respectively 114.9 and 114.6mAh/g under the 10C multiplying power, and the same terms is the single-phase LiCoO of preparation down
2Capacity then be respectively 71.4 and 69.8mAh/g.
Embodiment 7 is with Li
2CO
3And MnO
2And AgNO
3Mix in the alcohol medium by 1: 2: 0.175 mol ratio, in 800 ℃ of air or oxidizing atmosphere, behind the insulation 8h, naturally cool to room temperature.With the resulting 95wt%LiMn of above-mentioned synthetic method
2O
4/ 5wt%Ag composite granule is levigate, makes slurry by 85: 7: 8 weight ratio with acetylene black and Kynoar (PVDF) in the NMP medium, coats on the aluminium foil and carries out drying, the film of making thus is for anodal, metallic lithium foil is a negative pole, and the Celgard polypropylene screen is a barrier film, with LiPF
6-PC+DMC (1: 1) is an electrolyte, discharges and recharges test, is respectively 118 and 116mAh/g in the 2nd time between 3.5-4.5V voltage under the 5C multiplying power and 10 discharge capacities, and the same terms LiMn of preparation down
2O
4Corresponding each time specific capacity of powder is respectively 102 and 93.5mAh/g.
Embodiment 8 is with Li
2CO
3, NiO, MnO
2And AgNO
3By 1: 1: 1: 0.93 mol ratio mixed in deionized water, behind 1000 ℃ of air or oxidizing atmosphere insulation 10h, naturally cooled to room temperature and obtained 95wt%LiNi
1/2Mn
1/2O
2/ 5wt%Ag composite granule, the levigate back of composite material that above-mentioned synthetic method obtains is made slurry by 88: 5: 7 weight ratio with acetylene black and Kynoar (PVDF) in the NMP medium, coat on the aluminium foil and carry out drying, the film of making thus is for anodal, metallic lithium foil is a negative pole, the Celgard polypropylene screen is a barrier film, with LiPF
6-PC+DMC (1: 1) is an electrolyte, discharges and recharges test, is respectively 173.2 and 171.9mAh/g in the 2nd time between 2.5-4.5V voltage under the 5C multiplying power and 10 discharge capacities, and the same terms LiMn of preparation down
2O
4Corresponding each time specific capacity of powder is respectively 168.7 and 151.5mAh/g.
Embodiment 9 is with Li
2CO
3, NiO, Co
3O
4, MnO
2And AgNO
3By 1.49: 3: 1: 1: 0.111 mol ratio mixed in the alcohol medium, behind the insulation 8h, naturally cooled to room temperature and obtained 96wt%LiNi in 900 ℃ of air or oxidizing atmosphere
1/3Co
1/3Mn
1/3O
2/ 4wt%Ag composite granule, the levigate back of composite material that above-mentioned synthetic method obtains is made slurry by 85: 7: 8 weight ratio with acetylene black and Kynoar (PVDF) in the NMP medium, coat on the aluminium foil and carry out drying, the film of making thus is for anodal, metallic lithium foil is a negative pole, the Celgard polypropylene screen is a barrier film, with LiPF
6-PC+DMC (1: 1) is an electrolyte, discharges and recharges test, is respectively 143.4 and 139.5mAh/g in the 2nd time between 2.5-4.3V voltage under the 5C multiplying power and 10 discharge capacities, and the same terms LiMn of preparation down
2O
4Corresponding each time specific capacity of powder is respectively 138.7 and 115.5mAh/g.
For ease of comparing, corresponding preparation condition of above-mentioned each example and performance are summarized in the table 1, and degradation in capacity rate wherein is than being illustrated in degradation in capacity percentage that a certain discharge-rate lower substrate compound compares with the 2nd time for the 10th time and the same terms ratio of the degradation in capacity percentage of the composite material of preparation down.
The comparison of the various composite materials of table 1 and its matrix compounds high magnification degradation in capacity performance
| Matrix compounds | The composite material chemical formula | Preparation method and used raw material | Discharge-rate | Degradation in capacity rate ratio |
| Li 4Ti 50 12 | 96wt％Li 4Ti 5O 12/4wt％Ag | Synthetic method (Li 2CO 3+ rutile TiO 2+AgNO 3 ) | 4 | 2.6 |
| Li 4Ti 5O 12 | 96wt％Li 4Ti 5O 12/4wt％Ag | Synthetic method (Li 2CO 3+ Detitanium-ore-type TiO 2+AgO 2) | 4 | 29.6 |
| Li 4Ti 5O 12 | 8wt％Li 4Ti 5O 12/2wt％Ag | Synthetic method (Li 2CO 3+ rutile TiO 2+AgNO 3) | 4 | 9.O |
| LiCoO 2 | 97wt％LiCoO 2/3wt％Ag | Synthetic method (Li 2CO 3+Co 3O 4+Ag 2O) | 8 | 4.5 |
| LiCoO 2 | 95wt％LiCoO 2/5wt％Ag | Synthetic method (Li 2CO 3+Co 3O 4+AgNO 3) | 8 | 6.2 |
| LiCoO 2 | 95wt％LiCoO 2/5wt％Ag | Decomposition method (LiCoO 2+AgNO 3) | 10 | 8.6 |
| LiMn 2O 4 | 95wt％LiMn 2O 4/5wt％Ag | Synthetic method (Li 2CO 3+MnO 2+AgNO 3) | 5 | 4.9 |
| LiNi 1/2Mn 1/2O 2 | 95wt％LiNi 1/2Mn 1/2O 2/5wt％Ag | Synthetic method (Li 2CO 3+NiO+MnO 2+AgNO 3) | 5 | 13.6 |
| LiNi 1/3Co 1/3Mn 1/3O 2 | 96wt％LiNi 1/3Co 1/3Mn 1/3O 2/4wt％Ag | Synthetic method (Li 2CO 3+NiO+Co 3O 4+MnO 2+AgNO 3) | 5 | 6.2 |
| LiNi 1/3Co 1/3Mn 1/3O 2 | 95wt％LiNi 1/3C0 1/3Mn 1/3O 2/5wt％Ag | Decomposition method (LiNi 1/3Co 1/3Mn 1/3O 2+Ag 2O) | 10 | 3.6 |
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100664899A CN1332459C (en) | 2004-09-17 | 2004-09-17 | Lithium secondary cell composite electrode material capable of high power discharging and charging and preparing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100664899A CN1332459C (en) | 2004-09-17 | 2004-09-17 | Lithium secondary cell composite electrode material capable of high power discharging and charging and preparing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1588677A CN1588677A (en) | 2005-03-02 |
| CN1332459C true CN1332459C (en) | 2007-08-15 |
Family
ID=34604016
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100664899A Expired - Fee Related CN1332459C (en) | 2004-09-17 | 2004-09-17 | Lithium secondary cell composite electrode material capable of high power discharging and charging and preparing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1332459C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101609883B (en) * | 2009-07-13 | 2011-01-05 | 北京安华联合能源科技有限责任公司 | Preparation method of nano-silver particle dispersed Li4Ti5O12 thin film lithium ion battery negative electrode |
| CN107591532B (en) * | 2017-08-22 | 2020-05-19 | 中航锂电（洛阳）有限公司 | Aluminum fluoride/silver double-layer coated nickel-cobalt lithium manganate positive electrode material and preparation method thereof |
| CN108172814B (en) * | 2018-02-02 | 2020-04-24 | 云南民族大学 | Silver simple substance coated spinel type LiMn2O4Composite material and preparation method thereof |
| CN115528246A (en) * | 2021-06-25 | 2022-12-27 | 南京理工大学 | Secondary battery based on light-assisted plasma enhanced photoelectric property |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09147836A (en) * | 1995-11-22 | 1997-06-06 | Sanyo Electric Co Ltd | Lithium secondary battery |
| JP2000072444A (en) * | 1998-09-03 | 2000-03-07 | Shin Kobe Electric Mach Co Ltd | Lithium manganate and organic electrolyte secondary battery using the same |
| US6733923B2 (en) * | 2000-02-26 | 2004-05-11 | Korea Institute Of Science And Technology | Metal oxide electrode coated with porous metal film, porous metal oxide film or porous carbon film, its fabrication method, and lithium-ion secondary battery using it |
-
2004
- 2004-09-17 CN CNB2004100664899A patent/CN1332459C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09147836A (en) * | 1995-11-22 | 1997-06-06 | Sanyo Electric Co Ltd | Lithium secondary battery |
| JP2000072444A (en) * | 1998-09-03 | 2000-03-07 | Shin Kobe Electric Mach Co Ltd | Lithium manganate and organic electrolyte secondary battery using the same |
| US6733923B2 (en) * | 2000-02-26 | 2004-05-11 | Korea Institute Of Science And Technology | Metal oxide electrode coated with porous metal film, porous metal oxide film or porous carbon film, its fabrication method, and lithium-ion secondary battery using it |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1588677A (en) | 2005-03-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11855285B2 (en) | Full-gradient nickel cobalt manganese positive electrode material, ruthenium oxide coated material and preparation method thereof | |
| CN102339998B (en) | A kind of anode material for lithium-ion batteries and preparation method thereof | |
| KR100430938B1 (en) | Cathode material for lithium secondary battery and mathod for manufacturing the same | |
| EP3557668A1 (en) | Ternary material and preparation method therefor, battery slurry, positive electrode, and lithium battery | |
| CN104953199B (en) | Metal-doped nickle cobalt lithium manganate using lithium ion cell anode waste synthesis and its production and use | |
| CN113603154B (en) | High-voltage nickel-cobalt-manganese ternary precursor and preparation method thereof | |
| CN104993121B (en) | A kind of nickel manganese blending anode material for lithium-ion batteries and preparation method thereof | |
| CN111403729A (en) | Sodium ion battery positive electrode material, preparation method thereof and sodium ion battery | |
| CN101771145B (en) | Method for preparing multielement cathode materials for lithium ion batteries | |
| CN107359334A (en) | Spherical or spherical anode material for lithium-ion batteries and lithium ion battery | |
| CN103794776B (en) | A kind of high voltage, high-pressure solid lithium ion battery composite cathode material and preparation method | |
| CN113845153A (en) | Multi-element high-entropy solid solution cathode material and preparation method and application thereof | |
| CN101022161A (en) | Lithiumion secondary battery anode material LixCoyLazMn(z-y-z) O4 and producing process thereof | |
| CN113611839A (en) | Novel mixed system lithium-rich manganese-based positive plate and preparation method thereof, and lithium ion battery | |
| WO2024124723A1 (en) | Lithium cobaltate positive electrode material and preparation method therefor | |
| CN115010186A (en) | High-capacity oxygen valence-variable sodium ion battery positive electrode material and preparation method thereof | |
| CN110233261B (en) | A preparation method of single crystal ternary lithium battery positive electrode material and lithium ion battery | |
| CN102163709B (en) | Cobalt nickel manganese lithium oxide-cooper oxide compound positive material for lithium ion battery and preparation method thereof | |
| CN103413928B (en) | High-capacity high-compaction metal oxide anode material and preparation method thereof | |
| CN101582497B (en) | A kind of preparation method of high-capacity lithium-ion battery composite cathode material | |
| CN102983324B (en) | Positive material of AZO-coated lithium nickel manganese oxide secondary lithium battery and preparation method of positive pole material | |
| CN109461930B (en) | Gradient-structured multi-component material for lithium ion battery and preparation method thereof | |
| WO2024168990A1 (en) | Lithium-cobalt composite oxide and preparation method therefor and use thereof | |
| CN110563052A (en) | preparation method of carbon and lanthanum oxide co-coated modified lithium nickel manganese oxide positive electrode material | |
| CN1332459C (en) | Lithium secondary cell composite electrode material capable of high power discharging and charging and preparing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070815 Termination date: 20160917 |