CN1767239A - Lithium ferrite oxide/lithium ferrite nitride composite cathode material and its preparing method - Google Patents
Lithium ferrite oxide/lithium ferrite nitride composite cathode material and its preparing method Download PDFInfo
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- CN1767239A CN1767239A CNA2005100472573A CN200510047257A CN1767239A CN 1767239 A CN1767239 A CN 1767239A CN A2005100472573 A CNA2005100472573 A CN A2005100472573A CN 200510047257 A CN200510047257 A CN 200510047257A CN 1767239 A CN1767239 A CN 1767239A
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Abstract
The invention relates to a lithium ion cell cathode used lithium ferric oxide/ lithium ferric nitride compound material and its preparing method with reversible lithium capability Li2FeyO/Li3-xFexN, x=0.2-0.8, y=0.4-0.6. It adopts mechanical chemistry and high temperature solid phase reaction. The basic body material synthesizing and the compounding between the materials are finished at the same time; each group of the compound series is evenly scattered with better compatibility.
Description
Affiliated technical field
This present invention belongs to technical field of lithium ion,, body relates to a kind ofly has lithium ferrite oxide/lithium ferrite nitride compound system of height ratio capacity and preparation method thereof with mechanochemical reaction and high temperature solid-state method coupling preparation.
Background technology
For the miniaturization development of satisfying portable electric appts and the electric automobile widespread demand to the large-capacity high-power chemical power source, exploitation height ratio capacity, long-life lithium ion battery are important development directions of chemical power source.And traditional commercial li-ion battery electrode material is subjected to the restriction of performance own, has been difficult to make a breakthrough by updating manufacturing process again.Therefore become the hot issue of novel positive and negative electrode investigation of materials for the research and development of the height ratio capacity electrode material of lithium transition-metal oxide/carbon class system commonly used in the alternative present commercial material.
Metal oxide is an important branch of lithium ion battery negative material.As the M-O series of compounds (M=Co, Ni, Fe, Cu etc.) with rock salt structure, the Li that forms behind the embedding lithium
2O has electro-chemical activity, can reversible decomposition in circulation, and for having opened up a new direction that potential attraction is arranged in the lithium ion battery negative material field.Wherein Fe-O, Cu-O, Ni-O material are because elements such as Fe, the Cu in the system, Ni content in the earth's crust is abundant, and cheap characteristics are important directions of lithium ion battery electrode material research.Irreversible capacity is very high first but the irreversible structural change that produces in the process of removal lithium embedded first of such material directly causes it, has limited it and has further developed and use.Similarly, lithium metal oxide negative material such as Li
6Fe
2O
3Though it has higher theoretical capacity (up to 1000mAh/g), and its to the current potential of lithium below 1.1V, yet the restriction of removal lithium embedded mechanism (alloy mechanism) causes its high irreversibility of electrochemistry first still unavoidablely, lithium ion battery for anodal limited capacity, this undoubtedly can the too much positive electrode of loss, and the reversible capacity of battery is descended.
Summary of the invention
The objective of the invention is to, a kind of Li with good capacity compensating effect is provided
2Fe
yO/Li
3-xFe
xN compound system and preparation method thereof, angle from the capacity compensation, oxide, lithiumation thing with fe or iron are pre-reaction material, adopt mechanochemical reaction and high temperature solid state reaction coupling, prepare the lithium ferrite oxide/lithium ferrite nitride compound system with reversible removal lithium embedded performance, synthetic compound two processes with storeroom of basis material are finished simultaneously.This system has good capacity compensating effect, and material not only has higher capacity, can also utilize simultaneously himself abundant lithium source that the capacitance loss that irreversible change first causes is compensated.
The technical solution adopted for the present invention to solve the technical problems is: a kind of lithium ferrite oxide/lithium ferrite nitride composite cathode material, to form by oxide/lithium ferrite and lithium iron-nitride, and the chemical formula of oxide/lithium ferrite is Li
2Fe
yO, the chemical formula of lithium iron-nitride are Li
3-xFe
xN, Li
2Fe
yO and Li
3-xFe
xN is reversably removal lithium embedded material, wherein the y value between 0.4～0.6, Li
3-xFe
xN and Li
2Fe
yThe mol ratio of O is between 1: 1～1: 4.
Adopt mechanochemistry (high-energy ball milling) and high temperature solid state reaction coupling, wherein the preparation of mechanochemical reaction realization material and compound two processes of two kinds of materials are finished synchronously, high temperature solid state reaction is realized the composite material interface optimization in Properties, and its concrete preparation process is as follows:
(1) metal lithium sheet is at N
2Be prepared into the lithium nitride powder after heat treatment and grinding are sieved in the atmosphere;
(2) pre-reaction material of preparation oxide/lithium ferrite places ball grinder, and ball milling is 10～30 hours in Ar atmosphere, and the ball milling scope is controlled between 350 rev/mins～600 rev/mins, obtains oxide/lithium ferrite;
(3) the oxide/lithium ferrite powder of gained places ball grinder in the pre-reaction material of preparation lithium iron-nitride and the step (2), in N
2Ball milling is 10～30 hours in the atmosphere, and the pre-reaction material of described preparation lithium iron-nitride is the lithium nitride powder described in reduced iron powder, the step (1);
(4) with the powder in the step (3) between 650～750 ℃, in N
2Heat treatment is 0.5～2.5 hour under the atmosphere protection; Reaction finishes.
Preparation oxide/lithium ferrite Li
2Fe
yThe pre-reaction material of O is Li
2O or Li
2CO
3With reduction Fe powder or reduced iron powder and Fe
2O
3The mixture of powder, the middle Li of pre-reaction material: Fe element mol ratio is 2: 0.4～0.6;
The milling atmosphere of preparation oxide/lithium ferrite is an Ar gas;
With reduced iron powder, lithium nitride powder and oxide/lithium ferrite powder is reactive material, and the preparation of lithium iron-nitride and the preparation process of composite material adopt mechanochemistry technology to finish synchronously.
Reduced iron powder, lithium nitride powder and oxide/lithium ferrite powder, three's concrete molar ratio range is 0.3～0.9: 1: 1～4; Reduced iron powder, lithium nitride powder and oxide/lithium ferrite powder are that the mechanical milling process of reactant is at N
2Finish under the atmosphere protection.
Oxide, lithiumation thing with fe or iron are pre-reaction material, by the effect of mechanochemistry and high temperature solid state reaction, form the composite negative pole material system with good electrical electronic conductivity and high degree of dispersion type.Compound two processes of the preparation of material and storeroom are finished simultaneously, and the system that guaranteed has good dispersiveness and interface compatibility.Mechanochemical reaction is meant high-energy ball milling technology, Li
2Fe
yO, Li
3-xFe
xThe synthetic and compound of N all realized by this technology; High temperature solid state reaction is meant at N
2The heat treatment of carrying out under the gas shiled, high temperature solid state reaction can promote the counterdiffusion of two phase materials, thereby improves the interface performance of material.
Li
3-xFe
xN this as active electrode material, can to system first the irreversible capacity in the removal lithium embedded process effectively compensate.The Fe powder can partly substitute Li as a kind of important pre-reaction material
3Lithium among the N generates Li
3-xFe
xN, and be scattered in the compound system to improve the whole electron conduction ability of system as a kind of effective electronic conductor.
In the first charge-discharge process, Li in the compound system
2Fe
xO loses activity the lithium that is partially submerged into because the variation of irreversible structure and composition takes place alloying action, and reversible capacity is low first thereby caused it, and Li
3-xFe
xN is owing to be rich in lithium, and has good structural stability, therefore can effectively compensate Li
2Fe
yThe irreversible capacity that the decomposition of O and structural transformation cause, thereby the invertibity of raising system and stability; Consider the cooperative effect between component, Li in the compound system provided by the invention
3-xFe
xN and Li
2Fe
yThe mol ratio of O is between 1: 1～1: 4;
Described mechanochemical reaction is meant high-energy ball milling technology, Li
2Fe
yO, Li
3-xFe
xThe synthetic and compound of N all realized by this technology; Described high temperature solid state reaction is meant at N
2The heat treatment of carrying out under the gas shiled, high temperature solid state reaction can promote the counterdiffusion of two phase materials, thereby improves the interface performance of material.
Of the present invention really is to adopt the Li of mechanochemical reaction and high temperature solid state reaction coupling preparation with beneficial effect
2Fe
yO/Li
3-xFe
xN compound system, its lithium storage content all apparently higher than the carbon in lithium ion battery class negative material of present commercialization, are uniformly dispersed between each component in the system, have good compatibility and capacity compensating action, the coulombic efficiency height.In addition, its voltage platform also is higher than common carbon class negative material, can effectively suppress lithium metal dendrite like this separating out of negative terminal surface, and improves battery security.
Description of drawings
The present invention is further described below in conjunction with drawings and Examples.
The charging and discharging curve second time of the composite material of Fig. 1 embodiment one preparation and carbonaceous mesophase spherules (CMS) compares.Abscissa is a specific discharge capacity, the mAhg of unit
-1Ordinate is a voltage, the unit volt
SEM (electron microscope) morphology analysis of the material of Fig. 2 embodiment two preparations
Embodiment
Embodiment one
Preparation Li
3N.Take by weighing the lithium sheet of 100mg, at N
2Under the atmosphere protection,, when the lithium sheet for the treatment of general metal white is transformed into kermesinus fully, takes out, and place the glove box that is full of Ar gas in 100 ℃ of heat treatment 15h.With agate mortar it is ground, and sieve, promptly get and test required Li with 200 purpose screen clothes
3The N powder.
Take by weighing mol ratio and be 1: 1: 2.5 Fe powder and Fe
2O
3Powder, Li
2CO
3, placing stainless steel jar mill, and in ball grinder, charge into Ar gas, ball milling is 30 hours under 450 rev/mins rotating speed.In the glove box that is full of Ar gas, take by weighing an amount of Li with 1: 1: 0.3 mol ratio
3N, ball milling product, reduced iron powder, and mix, place stainless steel jar mill, in ball grinder, charge into N
2, at room temperature, ball milling 20 hours.With this ball milling product in 650 ℃, N
2Behind the heat treatment 2h, promptly get required product in the atmosphere.
The product of preparation is made electrode slice according to pole piece preparation technology, does that with metal Li electrode is made button cell, and electrolyte is LiPF
6/ EC: DMC (1: 1, Vol).Test charging and discharging currents density is 0.24mA/cm
2, by charging/discharging voltage 0～3V.The material reversible capacity of preparation reaches more than the 450mAh/g, and coulombic efficiency reaches about 99%.
Embodiment two
Li
3The preparation of N is with embodiment one.With Li
2O and reduced iron powder are even with 3: 2 mixed in molar ratio, place stainless steel jar mill, in Ar atmosphere with 500 rev/mins rotating speed ball milling 20h.Take by weighing 0.45g ball milling product, 0.11gLi3N, 0.65g reduced iron powder place stainless steel jar mill, and charge into N in ball grinders
2Gas continues ball milling 20h, and promptly gets required product after press the heat treatment method processing of embodiment one.
Claims (7)
1, a kind of lithium ferrite oxide/lithium ferrite nitride composite cathode material is characterized in that, is made up of oxide/lithium ferrite and lithium iron-nitride, and the chemical formula of oxide/lithium ferrite is Li
2Fe
yO, the chemical formula of lithium iron-nitride are Li
3-xFe
xN, Li
2Fe
yO and Li
3-xFe
xN is reversably removal lithium embedded material, wherein the y value between 0.4～0.6, Li
3-xFe
xN and Li
2Fe
yThe mol ratio of O is between 1: 1～1: 4.
2, the method for preparing the described a kind of lithium ferrite oxide/lithium ferrite nitride composite cathode material of claim 1, it is characterized in that, adopt mechanochemical reaction and high temperature solid state reaction coupling, wherein the preparation of mechanochemical reaction realization material and compound two processes of two kinds of materials are finished synchronously, high temperature solid state reaction is realized the composite material interface optimization in Properties, and its concrete preparation process is as follows:
(1) metal lithium sheet is at N
2Be prepared into the lithium nitride powder after heat treatment and grinding are sieved in the atmosphere;
(2) pre-reaction material of preparation oxide/lithium ferrite places ball grinder, and ball milling is 10～30 hours in Ar atmosphere, and the ball milling scope is controlled between 350 rev/mins～600 rev/mins, obtains oxide/lithium ferrite;
(3) the oxide/lithium ferrite powder of gained places ball grinder in the pre-reaction material of preparation lithium iron-nitride and the step (2), in N
2Ball milling is 10～30 hours in the atmosphere, and the pre-reaction material of described preparation lithium iron-nitride is the lithium nitride powder described in reduced iron powder, the step (1);
(4) with the powder in the step (3) between 650～750 ℃, in N
2Heat treatment is 0.5～2.5 hour under the atmosphere protection, and reaction finishes.
3, according to the lithium ferrite oxide/lithium ferrite nitride composite cathode material preparation method described in the claim 2, it is characterized in that described preparation oxide/lithium ferrite Li
2Fe
yThe pre-reaction material of O is Li
2O or Li
2CO
3With reduction Fe powder or reduced iron powder and Fe
2O
3The mixture of powder, the middle Li of pre-reaction material: Fe element mol ratio is 2: 0.4～0.6.
According to the lithium ferrite oxide/lithium ferrite nitride composite cathode material preparation method described in the claim 2, it is characterized in that 4, the milling atmosphere of described preparation oxide/lithium ferrite is an Ar gas.
5, according to the lithium ferrite oxide/lithium ferrite nitride composite cathode material preparation method described in the claim 2, it is characterized in that, described is reactive material with reduced iron powder, lithium nitride powder and oxide/lithium ferrite powder, and the preparation of lithium iron-nitride and the preparation process of composite material adopt mechanochemistry technology to finish synchronously.
6, according to the lithium ferrite oxide/lithium ferrite nitride composite cathode material preparation method described in the claim 2, it is characterized in that, described reduced iron powder, lithium nitride powder and oxide/lithium ferrite powder, three's concrete molar ratio range is 0.3～0.9: 1: 1～4.
According to the lithium ferrite oxide/lithium ferrite nitride composite cathode material preparation method described in the claim 2, it is characterized in that 7, described reduced iron powder, lithium nitride powder and oxide/lithium ferrite powder are that the mechanical milling process of reactant is at N
2Finish under the atmosphere protection.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100472573A CN1333477C (en) | 2005-09-17 | 2005-09-17 | Lithium ferrite oxide/lithium ferrite nitride composite cathode material and its preparing method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100472573A CN1333477C (en) | 2005-09-17 | 2005-09-17 | Lithium ferrite oxide/lithium ferrite nitride composite cathode material and its preparing method |
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| Publication Number | Publication Date |
|---|---|
| CN1767239A true CN1767239A (en) | 2006-05-03 |
| CN1333477C CN1333477C (en) | 2007-08-22 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113614032A (en) * | 2019-03-29 | 2021-11-05 | 古河机械金属株式会社 | Lithium nitride composition for sulfide-based inorganic solid electrolyte material |
| CN116216652A (en) * | 2023-01-17 | 2023-06-06 | 北京恩力动力技术有限公司 | Preparation method of lithium sulfide |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH113707A (en) * | 1997-06-11 | 1999-01-06 | Matsushita Denchi Kogyo Kk | Lithium secondary battery |
| WO2001022520A1 (en) * | 1999-09-24 | 2001-03-29 | Matsushita Electric Industrial Co., Ltd. | Lithium cell |
| JP2003338282A (en) * | 2002-05-21 | 2003-11-28 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte secondary battery |
| CN1258239C (en) * | 2003-05-19 | 2006-05-31 | 中国科学院青海盐湖研究所 | Method for producing lithium ion cell negative electrode material |
-
2005
- 2005-09-17 CN CNB2005100472573A patent/CN1333477C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113614032A (en) * | 2019-03-29 | 2021-11-05 | 古河机械金属株式会社 | Lithium nitride composition for sulfide-based inorganic solid electrolyte material |
| CN116216652A (en) * | 2023-01-17 | 2023-06-06 | 北京恩力动力技术有限公司 | Preparation method of lithium sulfide |
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