CN1300872C - Columnar structure LiCoO2 electrode material and its preparing process - Google Patents
Columnar structure LiCoO2 electrode material and its preparing process Download PDFInfo
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- CN1300872C CN1300872C CNB2005100117143A CN200510011714A CN1300872C CN 1300872 C CN1300872 C CN 1300872C CN B2005100117143 A CNB2005100117143 A CN B2005100117143A CN 200510011714 A CN200510011714 A CN 200510011714A CN 1300872 C CN1300872 C CN 1300872C
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Abstract
本发明提供了一种层柱结构钴酸锂电极材料及其制备方法，属理离子电池材料及其制备技术领域。该电极材料的化学组成为Lil-2βMβCoO2，钻与氧以共价键结合，构成CoO2主体层板，锂离子及过渡金属离子位于主体层板夹层，与带负电的主体层板以离子键结合，具有典型的α-NaFeO2型层状结构。本发明采用柠檬酸溶胶－凝胶方法制备出层状钴酸锂LiCoO2前驱体，再通过熔盐离子交换反应将层状钴酸锂中的部分锂离子用过渡金属离子Zn2+或Cd2+代替，然后通过焙烧使锂离子与过渡金属离子均匀分布在由CoO2构成的主体层板的夹层，获得层柱结构钴酸锂。其优点在于在充放电循环过程中具有更稳定的结构、更好的抗过充电性能、更高的比电容量及更佳的电化学循环性能。The invention provides a layer-column structure lithium cobalt oxide electrode material and a preparation method thereof, belonging to the technical field of ion battery materials and preparation thereof. The chemical composition of the electrode material is Li l-2β M β CoO 2 . Cobalt and oxygen are covalently bonded to form the main layer of CoO 2 . Lithium ions and transition metal ions are located in the interlayer of the main layer, and the negatively charged main layer The plates are bonded by ionic bonds and have a typical α- NaFeO2 -type layered structure. The present invention adopts the citric acid sol-gel method to prepare the layered lithium cobaltate LiCoO 2 precursor, and then converts part of the lithium ions in the layered lithium cobaltate with transition metal ions Zn 2+ or Cd 2 through molten salt ion exchange reaction. + Instead, lithium ions and transition metal ions are evenly distributed in the interlayer of the host laminate composed of CoO2 by firing to obtain a layer-column structure lithium cobaltate. Its advantage is that it has a more stable structure, better overcharge resistance, higher specific capacity and better electrochemical cycle performance during the charge-discharge cycle.
Description
Technical field
The invention belongs to lithium ion battery material and preparing technical field thereof, a kind of columnar structure LiCoO 2 electrode material and preparation method thereof particularly is provided, has replaced the columnar structure LiCoO 2 electrode material and the fused salt ion-exchange reactions preparation method thereof of lithium ion with doped transition metal ions.
Background technology
Has α-NaFeO
2The LiCoO of type layer structure
2Having excellent electrochemical properties the most in present various anode material for lithium-ion batteries, is the main positive electrode of commercialization lithium ion battery.But LiCoO
2Cost an arm and a leg actual specific capacity 120～140mAhg
-1, only be its theoretical capacity (274mAhg
-1) about 50%; LiCoO
2The anti-over-charging electrical property relatively poor, specific capacity reduces rapidly under higher charging voltage.For overcoming LiCoO
2The problem that exists, multiple modified measures and method have been taked in people's research.
It is to adopt Ni that present people study more method of modifying, Al, and Ti, multiple element such as Fe carries out doped and substituted to Co, in the hope of reaching the purpose of stabilizing material structure.As at document (1) Solid State Ionics, 2003, among the 159:241, people such as Chi-Hwan Han have synthesized Part of Co Al, the LiCo that Ni replaces
0.8M
0.2O
2(M=Al, Ni) compound, wherein LiCo
0.8Ni
0.2O
2Discharge capacity first reach 146mAh/g, 20 times circulation back capacity still remains on 130mAh/g.Many elements in the periodic table of elements have been used to the doped and substituted of Co, but except that the doped and substituted of only a few element (as Ni etc.) can not cause the reduction of reversible specific capacity first, the doped and substituted of other elements all can make its first reversible specific capacity reduce significantly, and the doped and substituted of elements such as Ni does not have obvious effect for the anti-over-charging electrical property that improves material.
Another important modification means are at LiCoO
2The surface coats Al
2O
3, P
2O
5, AlPO
4, materials such as MgO improve the pernicious interaction between electrode material and electrolyte, the dissolving that slows down cobalt.As at document (2) Solid State Ionics, 2002, among the 148:335, people such as Zhaoxiang Wang are at LiCoO
2The surface has coated MgO, Al
2O
3, SnO
2Deng metal oxide, wherein the product of MgO coating is 4.7V (vs.Li when charging by voltage
+/ still have good electrochemistry cycle performance Li) time.But metal oxides such as MgO all are the non-electrochemical active material, it adds the reduction that affiliation causes the electrode material reversible capacity, in addition, therefore the method does not change the body construction of material, is that the raising of electrochemistry cycle performance and anti-over-charging performance there is no remarkable effect to the structural stability of electrode material.
Stratiform LiCoO
2In charging process, with laminate interlayer Li
+Constantly deviating from of ion, repulsive force between the main body laminate strengthens, and the laminate spacing is constantly expanded, and when the laminate spacing increases to a certain degree (when promptly overcharging), laminate subsides, and irreversible transition takes place, and makes LiCoO
2Electrochemical specific capacity reduce rapidly.
Summary of the invention
The object of the present invention is to provide a kind of columnar structure LiCoO 2 electrode material and preparation method thereof, solved stratiform LiCoO
2What exist increases to a certain degree (when promptly overcharging) when the laminate spacing, and laminate subsides, and the generation irreversible transition makes LiCoO
2Electrochemical specific capacity reduce this problem rapidly.
Layer pole structure lithium cobaltate cathode material provided by the invention is with the part lithium ion Li in the stratiform cobalt acid lithium
+Use transition metal ions Zn
2+Or Cd
2+Replace.Its chemical composition general formula is Li
1-2 βM
βCoO
2, M is a kind of among transition metal Zn, the Cd in the formula, and 0.02≤β≤0.05; Cobalt and oxygen constitute CoO with covalent bonds
2Main body laminate, lithium ion and transition metal ions are positioned at body layer plate holder layer, combine with ionic bond with electronegative main body laminate, have typical α-NaFeO
2The type layer structure belongs to hexagonal crystal system, R 3m space group.
This layer post lithium cobaltate cathode material adopts fused salt ion-exchange reactions method to prepare.Promptly adopt the citric acid sol-gel process to prepare the stratiform cobalt acid lithium LiCoO of the tiny homogeneous of particle diameter earlier
2Presoma passes through the fused salt ion-exchange reactions then with the part lithium ion Li in the stratiform cobalt acid lithium
+Use transition metal ions Zn
2+Or Cd
2+Replace, by the roasting homogeneous lithium ion and transition metal ions are evenly distributed on by CoO again
2The interlayer of the main body laminate that constitutes obtains layer post cobalt acid lithium Li thus
1-2 βM
βCoO
2, wherein M is Zn, Cd.
Concrete processing step is as follows:
A is the mixed of 1.05～1.15/1/2.05～2.15 with lithium hydroxide, basic cobaltous carbonate and citric acid by Li/Co/ citric acid mol ratio, is dissolved in the deionized water, is made into Li
+Concentration be 2～4molL
-1Solution, in Rotary Evaporators, under the condition of 50～80 ℃ of temperature, 40～100rpm rotating speed, reacted 2～3 hours, form peony colloidal sol, be transferred in the vacuum drying chamber then, in 100～140 ℃ of vacuumizes 3～4 hours, obtain fluffy red xerogel, xerogel was obtained the floccule of pitchy in 2～5 hours 400～500 ℃ of preliminary treatment, be reentered in the Muffle furnace after the grinding, in 800～900 ℃ of following roastings 3～9 hours, obtain meeting the LiCoO of stoichiometric proportion and the tiny homogeneous of particle diameter
2
The LiCoO that B obtains steps A
2Is 1/5～1/15 mixed with having low-melting transition metal nitrate according to mol ratio, carries out the fused salt ion-exchange reactions being higher than under 10～30 ℃ of temperature of transition metal nitrate fusing point, and the reaction time is 0.5～3 hour; Used low-melting transition metal nitrate that has is: zinc nitrate hexahydrate Zn (NO
3)
26H
2O (36.4 ℃ of fusing points), four water cadmium nitrate Cd (NO
3)
24H
2A kind of among the O (59.4 ℃ of fusing points);
C has more than needed ion exchange product with the aprotic solvent flush away transition metal nitrate, vacuumize is 2～3 hours in 70～100 ℃ vacuum drying chamber; Used aprotic solvent is: acetone CH
3COCH
3, carbon tetrachloride CCl
4, cyclohexane C
6H
12In a kind of.
D with step C gained material with 2～10 ℃ of min
-1Speed was warming up to 300～500 ℃ and constant temperature 5～20 hours, naturally cooled to room temperature then, obtained a layer post cobalt acid lithium electrode material.
The invention has the advantages that: this layer post lithium cobaltate cathode material in the charge and discharge cycles process, lithium ion Li
+Can reversiblely take off embedding, and transition metal ions Zn
2+, Cd
2+Can not deviate from, play at the laminate interlayer and to stablize pillared effect, the architectural feature of maintenance electrode material, so a layer post cobalt acid lithium electrode material has more in the charge and discharge cycles process, and stable structure, better anti-over-charging electrical property, higher specific capacitance reach better electrochemistry cycle performance.
Embodiment
Embodiment 1:
With lithium hydroxide, basic cobaltous carbonate and citric acid is raw material, takes by weighing raw material and mixes in the ratio of Li/Co/ citric acid=1.05/1/2.05 (mol ratio), is dissolved in the deionized water, is made into Li
+Concentration be 4molL
-1Solution, (50 ℃, 100rpm) reaction is 2 hours in Rotary Evaporators, form peony colloidal sol, be transferred to then in the vacuum drying chamber,, obtain fluffy red xerogel in 100 ℃ of vacuumizes 4 hours, xerogel was obtained the floccule of pitchy in 2 hours 500 ℃ of preliminary treatment, be reentered into after the grinding in the Muffle furnace,, obtain meeting the LiCoO of stoichiometric proportion in 800 ℃ of following roastings 9 hours
2Product is as the presoma of fused salt ion-exchange reactions.
With zinc nitrate hexahydrate Zn (NO
3)
26H
2O and stratiform LiCoO
2Presoma is pressed the mixed of Zn/Li=5 (mol ratio), the reaction of heating and continuous stirring is 3 hours in 50 ℃ of water-baths, decompress filter and with acetone washing three times, filter cake was 70 ℃ of vacuumizes 3 hours, again 500 ℃ of roastings 5 hours, obtain product of the present invention, ICP and XRD test shows product consist of Li
0.95Zn
0.025CoO
2, belonging to hexagonal crystal system, Electrochemical results sees Table 1.
Embodiment 2:
With lithium hydroxide, basic cobaltous carbonate and citric acid is raw material, takes by weighing raw material and mixes in the ratio of Li/Co/ citric acid=1.1/1/2.1 (mol ratio), is dissolved in the deionized water, is made into Li
+Concentration be 2molL
-1Solution, (80 ℃, 60rpm) reaction is 3 hours in Rotary Evaporators, form peony colloidal sol, be transferred to then in the vacuum drying chamber,, obtain fluffy red xerogel in 140 ℃ of vacuumizes 3 hours, xerogel was obtained the floccule of pitchy in 5 hours 400 ℃ of preliminary treatment, be reentered into after the grinding in the Muffle furnace,, obtain meeting the LiCoO of stoichiometric proportion in 850 ℃ of following roastings 6 hours
2Product is as the presoma of fused salt ion-exchange reactions.
With zinc nitrate hexahydrate Zn (NO
3)
26H
2O and stratiform LiCoO
2Presoma is pressed the mixed of Zn/Li=15 (mol ratio), the reaction of heating and continuous stirring is 2 hours in 70 ℃ of water-baths, decompress filter and with acetone washing three times, filter cake was 100 ℃ of vacuumizes 2 hours, again 300 ℃ of roastings 20 hours, obtain product of the present invention, ICP and XRD test shows product consist of Li
0.90Zn
0.05CoO
2, belonging to hexagonal crystal system, Electrochemical results sees Table 1.
Embodiment 3:
With lithium hydroxide, basic cobaltous carbonate and citric acid is raw material, takes by weighing raw material and mixes in the ratio of Li/Co/ citric acid=1.15/1/2.15 (mol ratio), is dissolved in the deionized water, is made into Li
+Concentration be 3molL
-1Solution, (70 ℃, 60rpm) reaction is 3 hours in Rotary Evaporators, form peony colloidal sol, be transferred to then in the vacuum drying chamber,, obtain fluffy red xerogel in 120 ℃ of vacuumizes 4 hours, xerogel was obtained the floccule of pitchy in 4 hours 450 ℃ of preliminary treatment, be reentered into after the grinding in the Muffle furnace,, obtain meeting the LiCoO of stoichiometric proportion in 900 ℃ of following roastings 3 hours
2Product is as the presoma of fused salt ion-exchange reactions.
With four water cadmium nitrate Cd (NO
3)
24H
2O and stratiform LiCoO
2Presoma is pressed the mixed of Zn/Li=5 (mol ratio), the reaction of heating and continuous stirring is 2 hours in 70 ℃ of water-baths, decompress filter and with acetone washing three times, filter cake was 80 ℃ of vacuumizes 3 hours, again 400 ℃ of roastings 10 hours, obtain product of the present invention, ICP and XRD test shows product consist of Li
0.96Cd
0.02CoO
2, belonging to hexagonal crystal system, Electrochemical results sees Table 1.
Embodiment 4:
With lithium hydroxide, basic cobaltous carbonate and citric acid is raw material, takes by weighing raw material and mixes in the ratio of Li/Co/ citric acid=1.1/1/2.1 (mol ratio), is dissolved in the deionized water, is made into Li
+Concentration be 4molL
-1Solution, (60 ℃, 60rpm) reaction is 2 hours in Rotary Evaporators, form peony colloidal sol, be transferred to then in the vacuum drying chamber,, obtain fluffy red xerogel in 100 ℃ of vacuumizes 4 hours, xerogel was obtained the floccule of pitchy in 3 hours 450 ℃ of preliminary treatment, be reentered into after the grinding in the Muffle furnace,, obtain meeting the LiCoO of stoichiometric proportion in 850 ℃ of following roastings 6 hours
2Product is as the presoma of fused salt ion-exchange reactions.
With four water cadmium nitrate Cd (NO
3)
24H
2O and stratiform LiCoO
2Presoma is pressed the mixed of Zn/Li=15 (mol ratio), the reaction of heating and continuous stirring is 2 hours in 60 ℃ of water-baths, decompress filter and with acetone washing three times, filter cake was 90 ℃ of vacuumizes 2 hours, again 450 ℃ of roastings 10 hours, obtain product of the present invention, ICP and XRD test shows product consist of Li
0.9Cd
0.05CoO
2, belonging to hexagonal crystal system, Electrochemical results sees Table 1.
Adopt day island proper Tianjin ICPS-7500 type inductive coupling plasma emission spectrograph to measure the content of lithium, cobalt, zinc and cadmium in the product, day island proper Tianjin XRD-6000 type x-ray powder diffraction instrument (Cu K
αRadiation, λ=1.5406 ) characterize product structure, the Mastersizer of Britain Ma Erwen company 2000 type laser particle size analyzers are measured the particle diameter and the distribution of product.Test result shows: adopt the citric acid sol-gel process to prepare and meet LiCoO
2The stratiform cobalt of stoichiometric proportion acid lithium presoma, the chemical composition of the product that obtains by fused salt ion-exchange reactions method is Li
1-2 βM
βCoO
2(M=Zn, Cd); Presoma and ion-exchange afterproduct all belong to hexagonal crystal system, and have good crystal formation; Cobalt acid lithium presoma and the tiny homogeneous of ion-exchange afterproduct particle diameter, particle size distribution range 0.8～1.2 μ m, integrable cloth 1.0 μ m.
The synthetic layer post cobalt acid lithium Li of the inventive method will be adopted
1-2 βM
βCoO
2(M=Zn, Cd) electrode material and commercially available acetylene black conductive agent and polytetrafluoroethylene binding agent mix by the mass fraction of (85: 10: 5), and the thickness of compressing tablet to 100 μ m, in 120 ℃ of vacuum (＜1Pa) dry 24h.As to electrode, adopt Celgard 2400 barrier films, 1molL with metal lithium sheet
-1LiPF
6+ EC+DMC (EC/DMC volume ratio 1: 1) is an electrolyte, at the German M. Braun Unlab of company type dry argon gas glove box (H
2O＜1ppm, O
2＜be assembled into Experimental cell in 1ppm), adopt the blue electric BTI1-10 type cell tester in Wuhan to carry out electrochemical property test.The chemical composition of the layer post cobalt acid lithium sample that obtains by the embodiment of the invention, the electro-chemical test condition, the reversible specific discharge capacity when reaching circulation 10,20,30 times first is shown in Table 1.Comparative sample adopts the synthetic stratiform cobalt acid lithium LiCoO of citric acid sol-gel process for the present invention
2Presoma.Also listed the Electrochemical results that has the sample of higher chemical property in the bibliographical information in the table 1.
The composition of table 1 electrode material and electrochemistry cycle performance
| Sample | Chemical composition | Test condition | Reversible capacity mAhg -1 | |||
| First | 10 | 20 | 30 | |||
| Embodiment 1 | Li 0.95Zn 0.025CoO 2 | 3.0～4.3V，0.2mA·cm -2 | 153 | 148 | 146 | 144 |
| 3.0～4.5V，0.2mA·cm -2 | 176 | 172 | 170 | 167 | ||
| 3.0～4.7V，0.2mA·cm -2 | 209 | 195 | 192 | 190 | ||
| Embodiment 2 | Li 0.90Zn 0.05CoO 2 | 3.0～4.5V，0.2mA·cm -2 | 176 | 170 | 168 | 165 |
| 3.0～4.7V，0.2mA·cm -2 | 212 | 206 | 199 | 195 | ||
| Embodiment 3 | Li 0.96Cd 0.02CoO 2 | 3.0～4.5V，0.2mA·cm -2 | 179 | 176 | 173 | 171 |
| 3.0～4.7V，0.2mA·cm -2 | 213 | 199 | 197 | 194 | ||
| Embodiment 4 | Li 0.9Cd 0.05CoO 2 | 3.0～4.5V，0.2mA·cm -2 | 177 | 171 | 166 | 165 |
| 3.0～4.7V，0.2mA·cm -2 | 215 | 205 | 199 | 195 | ||
| Comparative sample | LiCoO 2 | 3.0～4.3V，0.2mA·cm -2 | 147 | 144 | 142 | 140 |
| 3.0～4.5V，0.2mA·cm -2 | 178 | 166 | 154 | 145 | ||
| 3.0～4.7V，0.2mA·cm -2 | 210 | 171 | ||||
| Document (1) | LiCoO 2 | 2.8～4.3V，70mA·g -1 | 139 | 122 | ||
| LiCo 0.8Ni 0.2O 2 | 2.8～4.3V，70mA·g -1 | 146 | 132 | |||
| Document (2) | LiCoO 2 | 2.5～4.5V，0.1mA·cm -2 | 190 | 80 | ||
| 2.5～4.7V，0.1mA·cm -2 | 265 | 100 | ||||
| MgO-LiCoO 2 | 2.5～4.5V，0.1mA·cm -2 | 170 | 160 | |||
| 2.5～4.7V，0.1mA·cm -2 | 210 | 195 | ||||
Remarkable result of the present invention as can be seen from Table 1 is: compare with adopting other element dopings replacement Co and surface coated method of modifying, the layer post cobalt acid lithium of the inventive method preparation can not cause the reduction of initial capacity, and has stable structure more, better anti-over-charging electrical property, higher specific capacitance and better electrochemistry cycle performance.
Claims (4)
1, a kind of columnar structure LiCoO 2 electrode material with doped transition metal ions replacement lithium ion, its chemical composition general formula is Li
1-2 βM
βCoO
2, M is a kind of among transition metal Zn, the Cd in the formula, and 0.02≤β≤0.05; Cobalt and oxygen constitute CoO with covalent bonds
2Main body laminate, lithium ion and transition metal ions are positioned at body layer plate holder layer, combine with ionic bond with electronegative main body laminate, have typical α-NaFeO
2The type layer structure belongs to hexagonal crystal system, R 3m space group.
2, a kind of method for preparing the described columnar structure LiCoO 2 electrode material of claim 1 is characterized in that: adopt the preparation of fused salt ion-exchange reactions method, promptly adopt citric acid so-gel method to prepare the stratiform cobalt acid lithium LiCoO of the tiny homogeneous of particle diameter earlier
2Presoma passes through the fused salt ion-exchange reactions then with the part lithium ion Li in the stratiform cobalt acid lithium
+Use transition metal ions Zn
2+Or Cd
2+Replace, by the roasting homogeneous lithium ion and transition metal ions are evenly distributed on by CoO again
2The interlayer of the main body laminate that constitutes obtains layer pole structure cobalt acid lithium Li thus
1-2 βM
βCoO
2
3, in accordance with the method for claim 2, it is characterized in that: processing step is as follows:
A, be the mixed of 1.05～1.15/1/2.05～2.15 by Li/Co/ citric acid mol ratio, be dissolved in the deionized water, be made into Li lithium hydroxide, basic cobaltous carbonate and citric acid
+Concentration be 2～4molL
-1Solution, in Rotary Evaporators, under the condition of 50～80 ℃ of temperature, 40～100rpm rotating speed, reacted 2～3 hours, form peony colloidal sol, be transferred to then in the vacuum drying chamber,, obtain fluffy red xerogel in 100～140 ℃ of vacuumizes 3～4 hours, xerogel was obtained the floccule of pitchy in 2～5 hours 400～500 ℃ of preliminary treatment, be reentered into after the grinding in the Muffle furnace,, obtain meeting LiCoO in 800～900 ℃ of following roastings 3～9 hours
2The cobalt acid lithium of stoichiometric proportion and the tiny homogeneous of particle diameter;
B, the LiCoO that step a is obtained
2Is 1/5～1/15 mixed with having low-melting transition metal nitrate according to mol ratio, carries out the fused salt ion-exchange reactions under the temperature that is higher than 10～30 ℃ of transition metal nitrate fusing points, and the reaction time is 0.5～3 hour;
C, with ion exchange product with aprotic solvent flush away transition metal nitrate more than needed, vacuumize is 2～3 hours in 70～100 ℃ vacuum drying chamber;
D, with step c gained material with 2～10 ℃ of min
-1Speed was warming up to 300～500 ℃ and constant temperature 5～20 hours, naturally cooled to room temperature then, obtained a layer post cobalt acid lithium Li
1-2 βM
βCoO
2
4, according to claim 2 or 3 described methods, it is characterized in that: described have low-melting transition metal nitrate and be: zinc nitrate hexahydrate Zn (NO
3)
26H
2O, four water cadmium nitrate Cd (NO
3)
24H
2A kind of among the O; Described aprotic solvent is: acetone CH
3COCH
3, carbon tetrachloride CCl
4Or cyclohexane C
6H
12In a kind of.
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| CN1508894A (en) * | 2002-12-16 | 2004-06-30 | 中国科学院成都有机化学研究所 | Positive electrode material for lithium ion cell and synthesizing method thereof |
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2005
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|---|---|---|---|---|
| US6368750B1 (en) * | 1998-07-13 | 2002-04-09 | Ngk Insulators, Ltd. | Lithium secondary battery |
| JP2002141063A (en) * | 2000-11-02 | 2002-05-17 | Toyota Central Res & Dev Lab Inc | Lithium secondary battery |
| CN1389939A (en) * | 2001-06-04 | 2003-01-08 | 中国科学院成都有机化学研究所 | Method of synthesizing LiCo1-xMxO2 as positive electrode material for lithium ion accmulator |
| JP2003221234A (en) * | 2001-11-22 | 2003-08-05 | Nippon Chem Ind Co Ltd | Lithium cobalt based composite oxide, method for producing the same, lithium secondary battery positive electrode active material, and lithium secondary battery |
| CN1506312A (en) * | 2002-12-11 | 2004-06-23 | 中国科学院成都有机化学研究所 | Prepn process of submicron level positive pole material for lithium ion cell |
| CN1508894A (en) * | 2002-12-16 | 2004-06-30 | 中国科学院成都有机化学研究所 | Positive electrode material for lithium ion cell and synthesizing method thereof |
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