CN100591624C - Coprecipitation-combustion synthesis method for lithium nickel cobalt manganate - Google Patents
Coprecipitation-combustion synthesis method for lithium nickel cobalt manganate Download PDFInfo
- Publication number
- CN100591624C CN100591624C CN200810002471A CN200810002471A CN100591624C CN 100591624 C CN100591624 C CN 100591624C CN 200810002471 A CN200810002471 A CN 200810002471A CN 200810002471 A CN200810002471 A CN 200810002471A CN 100591624 C CN100591624 C CN 100591624C
- Authority
- CN
- China
- Prior art keywords
- lithium
- nitrate
- acetate
- oxalate
- cobalt
- 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
Classifications
-
- 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
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a process of coprecipitation-combustion synthesis of nickel cobalt manganese lithium carbonate. (1) Utilizing acetate or nitrate of nickel, cobalt, and manganese as transitionmetal source and ammonia as complexing agent and utilizing H2C2O4, (NH4)3C2O4, (NH4)2CO3 or NH4HCO3 as precipitator, compound carbonate contained Ni-Co-Mn or oxalate precursors is synthesized by coprecipitation method. (2) Directly drying the compound carbonate containing Ni-Co-Mn or the suspension liquid of the oxalate and adding lithium nitrate or lithium acetate or a small quantity of water orethanol to adjust into rheological phase. (3) Laying the materials in rheological phase in an electric stove to perform burning synthesis reaction, wherein the electric stove heats the materials in rheological phase at temperature of 400-600DEG C and then keeps constant temperature. (4) Temper drawing the reaction product with temperature of 600-1200DEG C, and anode active materials of lithium ionbattery LiNixCoyMn1-x-yO2 is obtained. The invention has the advantages of simple technique, easy operation, saving water and energy and environment-friendliness, further, the synthetic material is provided with the shape of sphere or near-sphere, high specific capacity and fine cycle performance.
Description
Technical field
The present invention relates to a kind of synthetic method of anode material for lithium-ion batteries, particularly LiNi
xCo
yMn
1-x-yO
2Coprecipitation-combustion synthesis method.
Background technology
Existing commercial Li-ion batteries is most makes positive electrode material with cobalt acid lithium.Though that this material has is easily synthetic, stable performance and capacity be than advantages such as height, its synthetic required cobalt exist cost an arm and a leg, critical defects such as toxicity is big, scarcity of resources.Developing the positive electrode material that lacks cobalt or do not have cobalt becomes a direction of anode material for lithium-ion batteries development.
LiNi
xCo
yMn
1-x-yO
2It is one of being hopeful most of growing up in recent years novel anode material of replacing cobalt acid lithium.At present, synthetic LiNi
xCo
yMn
1-x-yO
2Method mainly contain coprecipitation method, sol-gel method, emulsion method, high temperature solid-state method and combustion method etc., wherein coprecipitation method is synthetic homogeneous phase LiNi
xCo
yMn
1-x-yO
2The general method of Shi Yonging; this method synthesis temperature is lower; can access sphere or class spheric particle; but owing to be difficult to transition metal ion be precipitated fully by certain precipitation agent; in the loss of filtering, easily cause in the washing process transition metal ion, and the synthetic presoma of existing coprecipitation method need carry out under atmosphere protection, and the concentration of stirring velocity, pH value, solution etc. influence bigger to the chemical property of synthetic product; to the equipment requirements height, be difficult to suitability for industrialized production.High temperature solid-state method is low for equipment requirements, but because raw material mixes the homogeneity can't reach molecular level, generally need be under comparatively high temps long-time calcining at constant temperature, production energy consumption is bigger, synthetic positive electrode material particle is random, and occurs dephasign easily, is difficult to synthetic homogeneous phase LiNi
xCo
yMn
1-x-yO
2Combustion method technology is simple, and is low for equipment requirements, and generated time is short, but the synthetic product particle is random, easily produces impurity such as NiO.
Summary of the invention
The object of the present invention is to provide a kind of simple to operately, generated time is short, synthesis temperature is low, be suitable for the method for suitability for industrialized production sphere or class ball-shaped lithium-ion battery anode material, i.e. LiNi
xCo
yMn
1-x-yO
2Coprecipitation-combustion synthesis method, the synthetic product has α-NaFeO
2The type laminate structure.
Concrete steps of the present invention are:
1) acetate or the nitrate with nickel, cobalt, manganese is transition metal source, is n (Ni): n (Co): n (Mn)=x: y in molar ratio: (1-x-y), and 0＜x＜1,0≤y＜0.5, x+y＜1; Accurately the weighing material adds mixing vinegar hydrochlorate or mixed nitrate salt brine solution that an amount of distilled water is made nickel, cobalt, manganese;
2) with ammoniacal liquor being complexing agent, is that the ammoniacal liquor of 1～5M joins in the above-mentioned solution with concentration, makes complex solution, and the consumption of ammoniacal liquor is mol ratio n (NH
3H
2O): n (Ni+Co+Mn)=1～7: 1, control pH value is between 5～9;
3) in above-mentioned complex solution, add precipitation agent H
2C
2O
4, (NH
4)
2C
2O
4, (NH
4)
2CO
3Or NH
4HCO
3, the consumption of precipitation agent is mol ratio n (C
2O
4 2-) or n (CO
3 2-): n (Ni+Co+Mn)=1.05～1.2: 1, make it at 25～80 ℃, stirring velocity is to react 0.5～5 hour in the 300-1000r/min water-bath device, obtains compound carbonate or the compound oxalate of Ni-Co-Mn;
4) regulate above-mentioned pH=7～9 that contain the suspension of Ni-Co-Mn compound carbonate or compound oxalate with ammoniacal liquor,, obtain the compound carbonate of Ni-Co-Mn or the mixture of oxalate and ammonium acetate or ammonium nitrate 100 ℃ of oven dry down;
5) do the lithium source with lithium nitrate or Lithium Acetate, in molar ratio n (Li): n (Ni+Co+Mn)=1.05～1.15: 1, accurately weighing lithium nitrate or Lithium Acetate join in the said mixture, and add less water or ethanol furnishing rheology phase;
7) the above-mentioned material that is the rheology phase is placed the also homothermic electric furnace that is heated to 400～600 ℃, make it to take place the self-propagating combustion reaction, obtain synthetic product;
8) with above-mentioned combustion reactions synthetic product 700～1200 ℃ of temper 10～25 hours, obtain having the anode material for lithium-ion batteries of good laminate structure and chemical property.
Described institute synthetic product is sphere or class spheric powder body material.
The present invention has following advantage and effect: when adopting coprecipitation method to prepare presoma, reactive material is dissolved in makes mixing solutions in the distilled water, realized the uniform mixing on the molecular level.Adopt carbonate or oxalate coprecipitation can synthesize nickel-cobalt-manganese compound carbonate or oxalate fast, institute's synthetic nickel-cobalt-manganese compound carbonate or oxalate chemical stability are good, and have sphere or class spheric profile, for synthesizing spherical or class spherical cathode material are had laid a good foundation.Adopt direct stoving process, eliminated coprecipitation method because the composition that washing causes loses, and saved a large amount of bath wateies.Be retained in the NH in the material
4 +Under certain conditions combustion reactions can take place with acetate and nitrate radical, the synthetic fuel that provides that burns is provided.Adopt rheology phase hybrid technique, help lithium salts and presoma uniform mixing.Adopt the low-temperature self-propagating combustion method, the acetate or the nitrate radical that have stayed when not only having made full use of synthetic presoma, and help shortening generated time.
The present invention had both overcome traditional co-precipitation method needs repeatedly filtration washing to cause the shortcoming that useful component runs off, water consumption is big, remedy the simple combustion method again, solid-phase synthesis institute synthetic positive electrode material particle shape is irregular and has occurred the deficiency of dephasign easily, have technology simply, operate easily, save water and energy, environmental protection, synthetic materials has spherical or advantage such as near-spherical pattern, specific storage height, good cycle.
Description of drawings
Fig. 1 is the LiNi of the present invention's preparation
1/3Co
1/3Mn
1/3O
2X-ray diffractogram.
Fig. 2 is the LiNi of the present invention's preparation
1/3Co
1/3Mn
1/3O
2Sem photograph.
Fig. 3 is the LiNi of the present invention's preparation
1/3Co
1/3Mn
1/3O
2Be assembled into 10 round-robin charging and discharging curve figure of battery for positive electrode active materials.
Embodiment:
Embodiment:
With Ni (CH
3COO)
24H
2O, Co (CH
3COO)
24H
2O and Mn (CH
3COO)
24H
2O, lithium nitrate are main raw material, and ammoniacal liquor is complexing agent, with H
2C
2O
4H
2O is a precipitation agent, adopts the synthetic LiNi of co-precipitation-combustion method
1/3Co
1/3Mn
1/3O
2
Operation steps:
1. press n (Ni): n (Co): n (Mn) (mol ratio)=1: 1: 1, accurately weighing Ni (CH
3COO)
24H
2O, Co (CH
3COO)
24H
2O and Mn (CH
3COO)
24H
2O adds an amount of distilled water and makes the mixing solutions that concentration is 1M;
2. add ammoniacal liquor to above-mentioned mixing solutions and make complex solution.
3. n (C in molar ratio
2O
4 2-): n (Ni+Co+Mn)=1.1: 1, accurately weighing H
2C
2O
4H
2O, being crushed into powder with the stone roller alms bowl joins in the above-mentioned complex solution.
4. the speed with 600r/min stirs in the water-bath device under 40 ℃, reaction 30nim.
5. regulate pH=8.5 with ammoniacal liquor, ageing 10nim then 100 ℃ of oven dry down, obtains the mixture of compound oxalate of nickel-cobalt-manganese and ammonium acetate.
6. n (Li): n (Ni+Co+Mn)=1.1: 1 in molar ratio, accurately the weighing lithium nitrate mixes and adds a spot of water furnishing rheology phase with the mixture of compound oxalate of above-mentioned nickel-cobalt-manganese and ammonium acetate;
7. the above-mentioned material that is the rheology phase is placed to be heated to 500 ℃ and homothermic electric furnaces, make it in electric furnace, to dewater, smolder, catch fire, series reaction such as burning.Internal reaction finished in 15 minutes.
8. reaction product is collected, fine ground, cross the alumina-ceramic crucible of packing into behind 50 mesh sieves, place electric furnace, 800 ℃ of temper 15 hours, furnace cooling then.
9. after the cooling, that synthetic product is fine ground, cross 300 mesh sieves, obtain having α-NaFeO
2The LiNi of type laminate structure and good electrical chemical property
1/3Co
1/3Mn
1/3O
2
Claims (4)
1, a kind of coprecipitation-combustion synthesis method of nickle cobalt lithium manganate is characterized in that concrete steps are:
1) acetate or the nitrate with nickel, cobalt, manganese is transition metal source, is n (Ni): n (Co): n (Mn)=x: y in molar ratio: (1-x-y), and 0＜x＜1,0≤y＜0.5, x+y＜1; Accurately the weighing material adds mixing vinegar hydrochlorate or mixed nitrate salt brine solution that an amount of distilled water is made nickel, cobalt, manganese;
2) with ammoniacal liquor being complexing agent, is that the ammoniacal liquor of 1～5M joins in the above-mentioned solution with concentration, makes complex solution, and the consumption of ammoniacal liquor is mol ratio n (NH
3H
2O): n (Ni+Co+Mn)=1～7: 1, control pH value is between 5～9;
3) in above-mentioned complex solution, add precipitation agent H
2C
2O
4, (NH
4)
2C
2O
4, (NH
4)
2CO
3Or NH
4HCO
3, the consumption of precipitation agent is mol ratio n (C
2O
4 2-) or n (CO
3 2-): n (Ni+Co+Mn)=1.05～1.2: 1, make it at 25～80 ℃, stirring velocity is to react 0.5～5 hour in the 300-1000r/min water-bath device, obtains compound carbonate or the compound oxalate of Ni-Co-Mn;
4) regulate above-mentioned pH=7～9 that contain the suspension of Ni-Co-Mn compound carbonate or compound oxalate with ammoniacal liquor,, obtain the compound carbonate of Ni-Co-Mn or the mixture of oxalate and ammonium acetate or ammonium nitrate 100 ℃ of oven dry down;
5) do the lithium source with lithium nitrate or Lithium Acetate, in molar ratio n (Li): n (Ni+Co+Mn)=1.05～1.15: 1, accurately weighing lithium nitrate or Lithium Acetate join in the said mixture, and add less water or ethanol furnishing rheology phase;
7) the above-mentioned material that is the rheology attitude is placed the also homothermic electric furnace that is heated to 400～600 ℃, make it to take place the self-propagating combustion reaction, obtain synthetic product;
8) with above-mentioned combustion reactions synthetic product 700～1200 ℃ of temper 10～25 hours, obtain having the anode material for lithium-ion batteries of good laminate structure and chemical property.
2. synthetic method as claimed in claim 1 is characterized in that institute's synthetic product is for having α-NaFeO
2The LiNi of type laminate structure
xCo
yMn
1-x-yO
2, 0＜x＜1,0≤y＜0.5, x+y＜1.
3. synthetic method as claimed in claim 1 is characterized in that institute's synthetic product is the spheric powder body material.
4. synthetic method as claimed in claim 1 is characterized in that institute's synthetic product is a class spheric powder body material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810002471A CN100591624C (en) | 2008-01-01 | 2008-01-01 | Coprecipitation-combustion synthesis method for lithium nickel cobalt manganate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810002471A CN100591624C (en) | 2008-01-01 | 2008-01-01 | Coprecipitation-combustion synthesis method for lithium nickel cobalt manganate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101215011A CN101215011A (en) | 2008-07-09 |
| CN100591624C true CN100591624C (en) | 2010-02-24 |
Family
ID=39621532
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810002471A Expired - Fee Related CN100591624C (en) | 2008-01-01 | 2008-01-01 | Coprecipitation-combustion synthesis method for lithium nickel cobalt manganate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100591624C (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101582500B (en) * | 2009-06-09 | 2011-03-30 | 厦门大学 | Method for preparing anode material of metal oxide nano-sheet lithium ion battery |
| CN102709544B (en) * | 2012-06-06 | 2015-04-15 | 中南大学 | Nickel cobalt lithium manganate composite cathode material and preparation method of nickel cobalt lithium manganate composite cathode material |
| CN102779992B (en) * | 2012-07-31 | 2015-08-26 | 浙江大学 | A kind of lithium ion battery positive electrode material in layer structure and preparation method thereof |
| CN102800870B (en) * | 2012-08-29 | 2015-02-25 | 浙江谷神能源科技股份有限公司 | Cylindrical power lithium-ion battery and preparation method |
| CN103066271B (en) * | 2013-01-14 | 2015-05-06 | 思伊纳化学科技（北京）有限公司 | High voltage lithium ion battery anode material and preparation method thereof |
| CN103400979A (en) * | 2013-08-05 | 2013-11-20 | 营口航盛科技实业有限责任公司 | Self-propagating combustion decomposition method for preparing LiaNixCoyMnzO2 anode material |
| CN104201368B (en) * | 2014-04-18 | 2017-03-08 | 宁夏东方钽业股份有限公司 | Lithium battery ternary material precursor nickel cobalt manganese hydroxide and preparation method thereof |
| CN103972487B (en) * | 2014-05-16 | 2016-08-24 | 厦门钨业股份有限公司 | A kind of multicomponent composite oxide material and industrial production process thereof |
| CN104218239B (en) * | 2014-08-21 | 2017-02-22 | 奇瑞汽车股份有限公司 | Preparation method for lithium nickel-cobalt manganate cathode material |
| CN104787805B (en) * | 2015-04-20 | 2016-09-14 | 齐鲁工业大学 | A kind of cobalt-lithium oxide and simple synthesis thereof |
| JP7004959B2 (en) * | 2016-07-14 | 2022-01-21 | 株式会社Ｇｓユアサ | Lithium transition metal composite oxide, transition metal hydroxide precursor, method for producing transition metal hydroxide precursor, method for producing lithium transition metal composite oxide, positive electrode active material for non-aqueous electrolyte secondary battery, non-aqueous electrolyte Electrodes for secondary batteries, non-aqueous electrolyte secondary batteries and power storage devices |
| CN106450263A (en) * | 2016-11-23 | 2017-02-22 | 昆明理工大学 | Method for preparing anode material for lithium ion batteries through oxalic acid pretreatment solid-phase method |
| CN108376770A (en) * | 2018-01-30 | 2018-08-07 | 南京红太阳新能源有限公司 | The preparation method of anode material for lithium-ion batteries |
| CN108288711A (en) * | 2018-02-12 | 2018-07-17 | 成都理工大学 | A kind of quaternary lithium-ion battery positive electrode material and preparation method |
| CN108832085A (en) * | 2018-06-05 | 2018-11-16 | 山东理工大学 | A kind of method that controllable low-temperature combustion method prepares lithium-rich anode material |
| CN110316769A (en) * | 2019-07-23 | 2019-10-11 | 铜陵金泰电池材料有限公司 | A method of anode material for lithium-ion batteries is prepared based on static mixer device |
| CN111446433A (en) * | 2020-04-23 | 2020-07-24 | 华鼎国联四川电池材料有限公司 | Positive electrode composite material for lithium battery and preparation method thereof |
| CN116119729A (en) * | 2021-11-12 | 2023-05-16 | 李龙 | Co-precipitation-combustion method for synthesizing high-voltage doped lithium manganate lithium ion battery anode material |
| CN114436344B (en) * | 2022-01-24 | 2023-07-07 | 广东邦普循环科技有限公司 | Preparation method and application of positive electrode material precursor with large channel |
-
2008
- 2008-01-01 CN CN200810002471A patent/CN100591624C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101215011A (en) | 2008-07-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100591624C (en) | Coprecipitation-combustion synthesis method for lithium nickel cobalt manganate | |
| CN105375010B (en) | A kind of preparation method of high compacted density lithium ion positive electrode | |
| CN101626080B (en) | Nickel-cobalt-manganese multiplex doped lithium ion battery anode material and preparation method thereof | |
| CN101621125B (en) | Nickel-cobalt-manganese multi-doped lithium ion battery cathode material and preparation method thereof | |
| CN102569780B (en) | Method for preparing lithium ion battery cathode material with layered structure | |
| CN101752553B (en) | Method for synthesizing cathode material LiNi0.5Mn1.5O4 for 5V lithium ion batteries | |
| US7985503B2 (en) | Method for preparing spherical nickelous hydroxide which is dopped and multiple metal oxides, and lithium ion secondary battery | |
| CN102386391B (en) | Method for preparing ternary complex anode material (LiNixCoyMn1-x-yO2) | |
| CN105958032B (en) | A kind of method and application improving zinc ferrite chemical property by doping nickel element | |
| CN108598466A (en) | A kind of preparation method for the nickel-cobalt-manganese ternary material for making constituent content distribution gradient | |
| CN105355905B (en) | A kind of preparation method of high voltage modification lithium-ion battery anode material nickel ion doped | |
| CN104362332B (en) | Preparation method of lithium-rich cathode material for lithium ion battery | |
| CN100495770C (en) | Lithiumion secondary battery anode material LixCoyLazMn(z-y-z) O4 and producing process thereof | |
| CN102208607A (en) | Synthesis and surface modification method of lithium excessive laminar oxide anode material | |
| CN104425815B (en) | The preparation method of high density spherical nickel-cobalt aluminic acid lithium material and its presoma | |
| CN101304090A (en) | Method for synthesizing lithium ion battery anode material LiNixCoyMn(1-x-y)O2 | |
| CN107528064A (en) | A kind of high voltage type class monocrystalline tertiary cathode material and preparation method thereof | |
| CN111640931A (en) | Preparation method of lithium-rich manganese-based positive electrode material | |
| CN106935824A (en) | A kind of preparation method of tertiary cathode material | |
| CN103794777A (en) | Preparation method of surface covered nickel lithium manganate positive electrode material | |
| CN104779385A (en) | High-specific capacity lithium ion battery cathode material and preparation method thereof | |
| CN106252594B (en) | A kind of ball-shaped lithium-ion battery anode material and its synthetic method with nanoscale two-phase coexistent structure | |
| CN103474640A (en) | Preparation method of lithium-rich manganese-based positive electrode material for lithium ion battery | |
| CN100429809C (en) | Method for preparing lithium - nickel - manganese - cobalt - oxygen anode material of lithium ion battery | |
| CN108807891A (en) | High potential anode material for lithium-ion batteries LiNi0.5-xMxMn1.5-ySiyO4And preparation 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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100224 Termination date: 20120101 |