CN1588677A - 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 PDF

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CN1588677A
CN1588677A CNA2004100664899A CN200410066489A CN1588677A CN 1588677 A CN1588677 A CN 1588677A CN A2004100664899 A CNA2004100664899 A CN A2004100664899A CN 200410066489 A CN200410066489 A CN 200410066489A CN 1588677 A CN1588677 A CN 1588677A
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electrode material
secondary cell
lithium secondary
high power
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CN1332459C (en
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温兆银
黄莎华
顾中华
朱修剑
徐孝和
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Shanghai Institute of Ceramics of CAS
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    • 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
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    • 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
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    • 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
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    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract

The invention relates to a kind of combination electrode material of lithium secondary cell white can high multiplying power charge and discharge and prepn. method. The characteristic is that combination electrode material is formed by lithium contained oxide with lithium ion ablating function and silver monomer, the composition general formula is (100-y)LimAnOx/YAg, Y means weight percentage ratio of combination material Ag, m, n and x are corresponding are corresponding mole quantities, the range is m=1-4, n=1-5, x=2-12, A is one of Ti, co, Ni, Mn or one of their mixed system, range of Y is 0.1-20 wt percent, Ag monomer is dispersed on crystal boundary to be used as conductive agent. The prepn. method of combination electrode material provided by the invention is to form second phase in process of composing matrix lithium embed oxide or by low-temp. decomposing presoma o f silver on base of matrix compound, capacity degeneracy ratio can reach 29.6.

Description

But the lithium secondary cell composite electrode material of high power charging-discharging and preparation method
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, when composite material 1C and 4C respectively capacity 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 Ag 2O 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.
Embodiment 10 will synthesize good LiNi 1/3Co 1/3Mn 1/3O 2Otide containing lighium thing and Ag 2O mixes in the alcohol medium by 1: 0.047 mol ratio, behind the insulation 10h, naturally cools to room temperature and obtains 95wt%LiNi in 300 ℃ of air or oxidizing atmosphere after 85 ℃ of oven dry 1/3Co 1/3Mn 1/3O 2/ 5wt%Ag composite granule, the levigate back of composite material that above-mentioned decomposition 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 129.3 and 127.5mAh/g in the 2nd time between 2.5-4.3V voltage under the 10C multiplying power and 10 discharge capacities, and the same terms LiNi of preparation down 1/3Co 1/3Mn 1/3O 2Corresponding each time specific capacity of powder is respectively 121.6 and 115.4mAh/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 5O 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 ????9.0
?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 1/3Co 1/3Mn 1/3O 2/5wt％Ag Decomposition method (LiNi 1/3Co 1/3Mn 1/3O 2+Ag 2O) ????10 ????3.6

Claims (9)

  1. But 1, the lithium secondary cell composite electrode material of a class high power charging-discharging is characterized in that it is to take off the otide containing lighium thing of embedding performance and the composite material that argent simple substance forms by having lithium ion, and it forms general formula is (100-y) Li mA nO x/ yAg represents that y is the percetage by weight of Ag in the combination electrode material in the formula, and m, n and x represent the molal quantity of respective element, and its scope is m=1-4, n=1-5, x=2-12; A is a kind of in Ti, Co, Ni, Mn or their mixed system, and the y scope is 0.1-20wt%.
  2. But 2,, it is characterized in that the y scope is 0.5-15wt% by the lithium secondary cell composite electrode material of the described high power charging-discharging of claim 1.
  3. But, it is characterized in that described to have the otide containing lighium thing that lithium ion takes off the embedding performance be Li 3, by the lithium secondary cell composite electrode material of claim 1 or 2 described high power charging-dischargings 4Ti 5O 12, LiCoO 2, LiMn 2O 4, LiNiO 2Or LiNi Y3Co Y3Mn Y3O 2In a kind of.
  4. But 4,, it is characterized in that Ag simple substance is dispersed on the crystal boundary, serves as conductive agent by the lithium secondary cell composite electrode material of claim 1 or 2 described high power charging-dischargings.
  5. But 5, the preparation method of the lithium secondary cell composite electrode material of a class high power charging-discharging, it is characterized in that it can adopt in following two kinds of methods any method preparation, these two kinds of preparation methods are respectively (1) forms second phase simultaneously in the building-up process of matrix compounds synthetic methods, and (2) predecessor by low-temperature decomposition silver on the basis of Manufactured matrix compounds forms the second silver-colored mutually decomposition method.
  6. But 6, press the preparation method of the lithium secondary cell composite electrode material of the described high power charging-discharging of claim 5, it is characterized in that the concrete processing step of synthetic method preparation in first is:
    1. by (100-y) Li mA nO x/ yAg general formula determines that the element of m, n, x occurrence and A is formed, and Ag predecessor doping, prepares burden;
    2. be medium with absolute ethyl alcohol or water, ball milling 4-8 hour, 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.
  7. But 7, press the preparation method of the lithium secondary cell composite electrode material of the described high power charging-discharging of claim 6, it is characterized in that described Ag predecessor is AgNO 3Or Ag 2O.
  8. But 8, press the preparation method of the lithium secondary cell composite electrode material of the described high power charging-discharging of claim 5, it is characterized in that the concrete processing step of second kind of decomposition method preparation 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.
  9. But 9, press the preparation method of the lithium secondary cell composite electrode material of the described high power charging-discharging of claim 8, it is characterized in that described Ag predecessor is AgNO 3Or Ag 2O.
CNB2004100664899A 2004-09-17 2004-09-17 Lithium secondary cell composite electrode material capable of high power discharging and charging and preparing method Expired - Fee Related CN1332459C (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
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
CN107591532A (en) * 2017-08-22 2018-01-16 中航锂电（洛阳）有限公司 A kind of aluminum fluoride/silver-colored double-coating nickel-cobalt lithium manganate cathode material and preparation method thereof
CN108172814A (en) * 2018-02-02 2018-06-15 云南民族大学 A kind of silver simple substance coating spinelle type LiMn2O4Composite material and preparation method thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
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
KR100324624B1 (en) * 2000-02-26 2002-02-27 박호군 Metal oxide electrodes coated with a porous metal film, a porous metaloxide film or a porous carbon film, its fabrication method and lithium secondary battery using it

Cited By (4)

* Cited by examiner, † Cited by third party
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
CN107591532A (en) * 2017-08-22 2018-01-16 中航锂电（洛阳）有限公司 A kind of aluminum fluoride/silver-colored double-coating nickel-cobalt lithium manganate cathode material and preparation method thereof
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
CN108172814A (en) * 2018-02-02 2018-06-15 云南民族大学 A kind of silver simple substance coating spinelle type LiMn2O4Composite material and preparation method thereof

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