CN104108699A - Preparation method of lithium ion battery graphite negative electrode material with high capacity and high compaction density - Google Patents
Preparation method of lithium ion battery graphite negative electrode material with high capacity and high compaction density Download PDFInfo
- Publication number
- CN104108699A CN104108699A CN201310161457.6A CN201310161457A CN104108699A CN 104108699 A CN104108699 A CN 104108699A CN 201310161457 A CN201310161457 A CN 201310161457A CN 104108699 A CN104108699 A CN 104108699A
- Authority
- CN
- China
- Prior art keywords
- graphite
- lithium ion
- ion battery
- preparation
- purification
- 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.)
- Pending
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
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of a lithium ion battery graphite negative electrode material with high capacity and high compaction density. The preparation method comprises the following steps: 1, carrying out spheroidization of natural graphite with the fixed carbon content of 80-99%; and 2, carrying out purification and graphitization, and thus obtaining the required graphite negative electrode material. The obtained material has high compaction density, the compaction density of a powder is 1.8-2.1 g/cm<3>, the compaction density of a pole piece is 1.75-1.95 g/cm<3>, the discharge specific capacity is high and greater than 370 mAh/g, the average particle size is 5-30 [mu]m, the liquid absorbing performance is good, and requirements of high specific capacity and high multiplying power of a lithium ion battery are fitted.
Description
Technical field
The present invention relates to a kind of preparation method of high compacted density graphite negative material of lithium ion battery.
Background technology
The electronic information epoch make the demand rapid growth to portable power source, because lithium ion battery has the significant advantage of high-voltage, heavy body, and have extended cycle life, safety performance is good, it is had broad application prospects in many-sides such as portable electric appts, electromobile, space technology, national defense industry, become the study hotspot of widely paying close attention in recent years.Current commercial lithium ion battery negative material is mainly carbon material, wherein natural graphite good conductivity, degree of crystallinity is high, have good laminate structure, the embedding-deintercalation that is applicable to lithium forms lithium-compound between graphite layers, and charge/discharge capacity is high, efficiency for charge-discharge is high, irreversible capacity is low, has good charge and discharge potential platform, becomes the negative material that current lithium ion battery applications is maximum.But the shortcoming of graphite material is also clearly, the one, graphite spacing d
002≤ 0.34nm, is less than the spacing d=0.37nm of graphite intercalation compound Li-GIC, causes in charge and discharge process, and graphite layers is apart from change, causes that graphite ink sheet peels off, efflorescence, causes electric cycle performance undesirable; The 2nd, poor with the consistency of electrolytic solution; The 3rd, its tap density is lower.In order to overcome the above-mentioned deficiency of graphite material, graphite material is carried out to modification and become the focus of carbon negative pole research in recent years.
From current present Research, the loading capacity performance of unit weight carbon material has approached theoretical value, therefore the in the situation that of battery given volume, if obtain higher energy density per unit volume, need higher compacted density, and existing material, under high compacting, under condition, there is imbibition deficiency, there is no enough passages that discharges and recharges, the problems such as diving that capacity is brought into play not exclusively and circulation is expanded, therefore around how to ensure that improving compacted density under the good prerequisite of heavy body cycle performance has launched research widely, as Xie Qiusheng, Qiao Yongmin etc. add catalyzed graphitization mode to be coated charing has made compacted density and has been not less than 1.70g/cm
3graphite cathode material (Chinese patent Granted publication CN102339988A), but the compacted density of its negative material making or not high enoughly (be less than 1.8g/cm
3), and capacity performance do not arrive 370mAh/g yet, fail to fully demonstrate the advantage of high compacting heavy body, and making processes bothers, cost is higher.
Summary of the invention
The object of this invention is to provide a kind of preparation method of high compacted density graphite negative material of lithium ion battery, the problem that solve is to make negative material have higher loading capacity and compacted density.
Material choice fixed carbon content, 80%～90%, needs enough impurity to ensure that it leaves corresponding hole while effusion; Nodularization can change its chemical property, then by purification of graphite, graphite-structure is become in order by unordered, has increased the describing property of itself and electrolytic solution, and the specific storage of material is brought into play better.
The present invention is by the following technical solutions: high ash content natural flake graphite is carried out to nodularization, make spherical graphite, again spherical graphite is carried out to high temperature purification and high temperature graphitization processing, the micropore that utilizes its ash content to overflow in the time of high temperature purification to stay obtains the high graphite cathode material that holds high compacting of a kind of porous;
Affiliated preparation method comprises the following steps:
(1) use ultramicron pelletizer to carry out nodularization to natural flake graphite, when nodularization, speed of grinding plate is 2000-4800rpm/min, and the nodularization time is 20-40min, makes the spherical graphite of median size 5-30 μ m;
(2) spherical graphite making being put into purification of graphite equipment processes; Concrete processing mode is material to be put into the plumbago crucible of body of heater, speed with 5-200 DEG C/min heats up, in the time that temperature in stove reaches 1000-1500 DEG C, flow with 1-5m3/h passes into nitrogen, continue to be warming up to 1500-2200 DEG C with the speed of 5-200 DEG C/min, pass into chlorine with the flow of 1-5m3/h simultaneously, until temperature stops heating while rising to 2200-3300 DEG C, insulation 5h, change again with the flow of 1-5m3/h and pass into nitrogen, 5-15h, purification of graphite process completes, and makes required graphite negative material of lithium ion battery.
The fixed carbon content of described natural flake graphite is 80%～90%, and median size is 60-100 μ m, and largest particle can pass through 80 eye mesh screens.
Described purification of graphite equipment is acheson furnace.
The graphite cathode material making by the present invention, compacted density is high, pole piece compacted density is between 1.75-1.95g/cm3, and powder body compacted density is between 1.8-2.1g/cm3, and specific discharge capacity is high, be greater than 370mAh/g, median size is 5-30 μ m, and absorbent is good, is applicable to current lithium ion battery to height ratio capacity and the forthright requirement of high power, and cheap, simple to operate.
Brief description of the drawings
Below in conjunction with the correlated performance of brief description of the drawings material of the present invention.
Fig. 1 is the ultramicron pelletizing structural scheme of mechanism that the present invention uses.Mark in figure: 1, chuck (heating, cooling), 2, stator, 3, circulation loop, 4, dog-house, 5, bleeder valve, 6, discharge port, 7, abrading block, 8, rotor.
Embodiment
Below in conjunction with embodiment, the present invention is described in further details
Embodiment 1
(1) to fixed carbon content be 90%, the natural flake graphite of median size 80 μ m uses ultramicron pelletizer to carry out nodularization, when nodularization, speed of grinding plate is 3000rpm/min, the nodularization time is 35min, makes the spherical graphite of median size 23 μ m; (2) spherical graphite making is put into purification of graphite equipment and process, processing mode is material to be put into the plumbago crucible of body of heater, heats up, with the speed of 20 DEG C/min in the time that the temperature of plumbago crucible in stove reaches 1000 DEG C, with 3m
3the flow of/h passes into nitrogen, continues to be warming up to 1500 DEG C with the speed of 50 DEG C/min, simultaneously with 3m
3the flow of/h passes into chlorine, until temperature stops heating while rising to 2000 DEG C, and insulation 5h, then change with 3m
3the flow of/h passes into nitrogen, 5h, and purification of graphite process completes.The negative material obtaining, loading capacity 370.5mAh/g, powder-compacting 1.92g/cm
3, pole piece compacted density 1.83g/cm
3.
Embodiment 2
(1) to fixed carbon content be 80%, the natural flake graphite of median size 90 μ m uses ultramicron pelletizer to carry out nodularization, when nodularization, speed of grinding plate is 4200rpm/min, the nodularization time is 30min, makes the spherical graphite of median size 17 μ m; (2) spherical graphite making is put into purification of graphite equipment and process, processing mode is material to be put into the plumbago crucible of body of heater, heats up, with the speed of 50 DEG C/min in the time that the temperature of plumbago crucible in stove reaches 1200 DEG C, with 3m
3the flow of/h passes into nitrogen, continues to be warming up to 1800 DEG C with the speed of 50 DEG C/min, simultaneously with 3m
3the flow of/h passes into chlorine, until temperature stops heating while rising to 2500 DEG C, and insulation 5h, then change with 3m
3the flow of/h passes into nitrogen, 10h, and purification of graphite process completes.The negative material obtaining, loading capacity 372.1mAh/g, powder-compacting 1.98g/cm
3, pole piece compacted density 1.88g/cm
3.
Embodiment 3
(1) to fixed carbon content be 85%, the natural flake graphite of median size 65 μ m uses ultramicron pelletizer to carry out nodularization, when nodularization, speed of grinding plate is 4500rpm/min, the nodularization time is 35min, makes the spherical graphite of median size 15 μ m; (2) spherical graphite making is put into purification of graphite equipment and process, processing mode is material to be put into the plumbago crucible of body of heater, heats up, with the speed of 50 DEG C/min in the time that the temperature of plumbago crucible in stove reaches 1500 DEG C, with 3m
3the flow of/h passes into nitrogen, continues to be warming up to 2000 DEG C with the speed of 50 DEG C/min, simultaneously with 3m
3the flow of/h passes into chlorine, until temperature stops heating while rising to 3200 DEG C, and insulation 5h, then change with 3m
3the flow of/h passes into nitrogen, 15h, and purification of graphite process completes.The negative material obtaining, loading capacity 370.2mAh/g, powder-compacting 2.01g/cm
3, pole piece compacted density 1.90g/cm
3.
Embodiment 4
(1) to fixed carbon content be 83%, the natural flake graphite of median size 70 μ m uses ultramicron pelletizer to carry out nodularization, when nodularization, speed of grinding plate is 4000rpm/min, the nodularization time is 35min, makes the spherical graphite of median size 19 μ m; (2) spherical graphite making is put into purification of graphite equipment and process, processing mode is material to be put into the plumbago crucible of body of heater, heats up, with the speed of 50 DEG C/min in the time that the temperature of plumbago crucible in stove reaches 1200 DEG C, with 3m
3the flow of/h passes into nitrogen, continues to be warming up to 1500 DEG C with the speed of 50 DEG C/min, simultaneously with 3m
3the flow of/h passes into freonll-11, until temperature stops heating while rising to 3200 DEG C, and insulation 5h, then change with 3m
3the flow of/h passes into nitrogen, 15h, and purification of graphite process completes.The negative material obtaining, loading capacity 371.1mAh/g, powder-compacting 2.07g/cm
3, pole piece compacted density 1.93g/cm
3.
Embodiment 5
(1) to fixed carbon content be 88%, the natural flake graphite of median size 75 μ m uses ultramicron pelletizer to carry out nodularization, when nodularization, speed of grinding plate is 4000rpm/min, the nodularization time is 30min, makes the spherical graphite of median size 21 μ m; (2) spherical graphite making is put into purification of graphite equipment and process, processing mode is material to be put into the plumbago crucible of body of heater, heats up, with the speed of 50 DEG C/min in the time that the temperature of plumbago crucible in stove reaches 1200 DEG C, with 3m
3the flow of/h passes into nitrogen, continues to be warming up to 1500 DEG C with the speed of 50 DEG C/min, simultaneously with 3m
3the flow of/h passes into chlorine, until temperature stops heating while rising to 3000 DEG C, and insulation 5h, then change with 3m
3the flow of/h passes into nitrogen, 15h, and purification of graphite process completes.The negative material obtaining, loading capacity 370.8mAh/g, powder-compacting 2.05g/cm
3, pole piece compacted density 1.91g/cm
3.
Table 1 is the DCO data of above-described embodiment
Claims (4)
1. the preparation method of a high compacted density graphite negative material of lithium ion battery, it is characterized in that: high ash content natural flake graphite is carried out to nodularization, make spherical graphite, again spherical graphite is carried out to high temperature purification and high temperature graphitization processing, the micropore that utilizes its ash content to overflow in the time of high temperature purification to stay obtains the high graphite cathode material that holds high compacting of a kind of porous;
Affiliated preparation method comprises the following steps:
(1) use ultramicron pelletizer to carry out nodularization to natural flake graphite, when nodularization, speed of grinding plate is 2000-4800rpm/min, and the nodularization time is 20-40min, makes the spherical graphite of median size 5-30 μ m;
(2) spherical graphite making being put into purification of graphite equipment processes; Concrete processing mode is material to be put into the plumbago crucible of body of heater, heats up, with the speed of 5-200 DEG C/min in the time that temperature in stove reaches 1000-1500 DEG C, with 1-5m
3the flow of/h passes into nitrogen, continues to be warming up to 1500-2200 DEG C with the speed of 5-200 DEG C/min, simultaneously with 1-5m
3the flow of/h passes into chlorine, until temperature stops heating while rising to 2200-3300 DEG C, and insulation 5h, then change with 1-5m
3the flow of/h passes into nitrogen, 5-15h, and purification of graphite process completes, and makes required graphite negative material of lithium ion battery.
2. the preparation method of high compacted density graphite negative material of lithium ion battery according to claim 1, it is characterized in that: the fixed carbon content of described natural flake graphite is 80%～90%, median size is 60-100 μ m, and largest particle can pass through 80 eye mesh screens.
3. the preparation method of high compacted density graphite negative material of lithium ion battery according to claim 1, is characterized in that: described purification of graphite equipment is acheson furnace.
4. the preparation method of high compacted density graphite negative material of lithium ion battery according to claim 1, it is characterized in that: gained graphite cathode material, median size is 5-30 μ m, pole piece compacted density is 1.75-1.95g/cm3, powder body compacted density is 1.8-2.1g/cm3, and specific discharge capacity is greater than 370mAh/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310161457.6A CN104108699A (en) | 2013-04-22 | 2013-04-22 | Preparation method of lithium ion battery graphite negative electrode material with high capacity and high compaction density |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310161457.6A CN104108699A (en) | 2013-04-22 | 2013-04-22 | Preparation method of lithium ion battery graphite negative electrode material with high capacity and high compaction density |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104108699A true CN104108699A (en) | 2014-10-22 |
Family
ID=51705718
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310161457.6A Pending CN104108699A (en) | 2013-04-22 | 2013-04-22 | Preparation method of lithium ion battery graphite negative electrode material with high capacity and high compaction density |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104108699A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105489893A (en) * | 2015-10-28 | 2016-04-13 | 江西正拓新能源科技股份有限公司 | Graphite anode material for lithium-ion battery and preparation method of graphite anode material |
| CN109652192A (en) * | 2019-01-11 | 2019-04-19 | 西安凯丰铁路机电设备有限公司 | A kind of aqua type coefficient of friction modifiers for rail tread |
| CN113161514A (en) * | 2020-01-07 | 2021-07-23 | 珠海冠宇电池股份有限公司 | Graphite composition, battery cathode and lithium ion battery |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1697215A (en) * | 2005-05-27 | 2005-11-16 | 深圳市贝特瑞电子材料有限公司 | Cathode material of composite carbon in use for lithium ion battery and preparation method |
| CN1702893A (en) * | 2005-04-20 | 2005-11-30 | 深圳市贝特瑞电子材料有限公司 | Cathode material of Li-ion battery and preparation method, battery cathode, battery thereof |
| CN1964113A (en) * | 2006-11-29 | 2007-05-16 | 武汉理工大学 | A bipolar plate for conductive ceramics/graphite proton exchange membrane fuel cell and its manufacture method |
| CN101323447A (en) * | 2008-07-21 | 2008-12-17 | 深圳市贝特瑞新能源材料股份有限公司 | Graphite powder of lithium ionic cell cathode and preparation thereof |
| CN102030326A (en) * | 2010-11-22 | 2011-04-27 | 中科恒达石墨股份有限公司 | Preparation method of graphite cathode material |
| CN102637859A (en) * | 2012-04-06 | 2012-08-15 | 宁德新能源科技有限公司 | Lithium ion battery, graphite cathode material of lithium ion battery, and preparation method of graphite anode material |
| WO2013029212A1 (en) * | 2011-09-03 | 2013-03-07 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium-ion battery negative electrode material, preparation method therefor, and lithium-ion battery |
-
2013
- 2013-04-22 CN CN201310161457.6A patent/CN104108699A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1702893A (en) * | 2005-04-20 | 2005-11-30 | 深圳市贝特瑞电子材料有限公司 | Cathode material of Li-ion battery and preparation method, battery cathode, battery thereof |
| CN1697215A (en) * | 2005-05-27 | 2005-11-16 | 深圳市贝特瑞电子材料有限公司 | Cathode material of composite carbon in use for lithium ion battery and preparation method |
| CN1964113A (en) * | 2006-11-29 | 2007-05-16 | 武汉理工大学 | A bipolar plate for conductive ceramics/graphite proton exchange membrane fuel cell and its manufacture method |
| CN101323447A (en) * | 2008-07-21 | 2008-12-17 | 深圳市贝特瑞新能源材料股份有限公司 | Graphite powder of lithium ionic cell cathode and preparation thereof |
| CN102030326A (en) * | 2010-11-22 | 2011-04-27 | 中科恒达石墨股份有限公司 | Preparation method of graphite cathode material |
| WO2013029212A1 (en) * | 2011-09-03 | 2013-03-07 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium-ion battery negative electrode material, preparation method therefor, and lithium-ion battery |
| CN102637859A (en) * | 2012-04-06 | 2012-08-15 | 宁德新能源科技有限公司 | Lithium ion battery, graphite cathode material of lithium ion battery, and preparation method of graphite anode material |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105489893A (en) * | 2015-10-28 | 2016-04-13 | 江西正拓新能源科技股份有限公司 | Graphite anode material for lithium-ion battery and preparation method of graphite anode material |
| CN109652192A (en) * | 2019-01-11 | 2019-04-19 | 西安凯丰铁路机电设备有限公司 | A kind of aqua type coefficient of friction modifiers for rail tread |
| CN113161514A (en) * | 2020-01-07 | 2021-07-23 | 珠海冠宇电池股份有限公司 | Graphite composition, battery cathode and lithium ion battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103094528B (en) | A kind of lithium ion power and energy-storage battery hard carbon cathode material and preparation method thereof | |
| CN103165862B (en) | A kind of high performance lithium ionic cell cathode material and preparation method thereof | |
| CN103346324B (en) | Lithium ion battery cathode material and its preparation method | |
| CN102169985B (en) | Preparation method of lithium ion battery carbon anode material | |
| CN104882607B (en) | A kind of Animal Bone base class graphene lithium ion battery negative material and preparation method thereof | |
| CN109742383A (en) | Sodium-ion battery hard carbon cathode material based on phenolic resin and its preparation method and application | |
| CN104009210B (en) | A kind of porous silicon/carbon composite material, Preparation method and use | |
| CN103579624B (en) | Modified lithium battery graphite crucible waste material negative material and preparation method thereof and application | |
| CN104659366A (en) | Preparation method of anode material for power lithium ion battery | |
| KR20130030769A (en) | Composite hard carbon material of negative electrode for lithium ion battery and method for preparing the same | |
| CN103094535A (en) | Sulfur/carbon porous nano composite material and preparation method and application thereof | |
| CN102881870A (en) | Lithium ion battery silicon substrate lithium salt composite negative electrode material and preparation method and application thereof | |
| CN105226285A (en) | A kind of porous silicon carbon composite and preparation method thereof | |
| CN104393298A (en) | Blocky graphite negative electrode material for lithium ion battery, preparation method of blocky graphite negative electrode material and lithium ion battery | |
| CN104600309A (en) | Preparation method of secondary start-up lithium ion battery cathode material | |
| CN106450189A (en) | Nitrogen-doped carbon-coated iron oxide negative electrode material for lithium-ion battery and preparation | |
| CN110518245A (en) | It is a kind of with water-absorbing resin prepare carbon material and its lithium-sulphur cell positive electrode in application | |
| CN104347858A (en) | Lithium ion secondary cell cathode active material and preparation method thereof, lithium ion secondary cell cathode pole piece and lithium ion secondary cell | |
| CN105702956A (en) | Negative material for sodium-ion battery and preparation method of negative material | |
| CN106935830A (en) | A kind of lithium ion battery composite cathode material and its preparation method and application | |
| CN111146423B (en) | Pre-lithiated binary topological structure phosphorus/carbon composite material and preparation method and application thereof | |
| CN109065873A (en) | A kind of preparation method and material of the mesoporous graphitic nitralloy carbon negative pole material of loaded nano-copper | |
| CN108987704A (en) | A kind of preparation method and applications of the silicon-carbon composite cathode material of lithium ion battery with porous structure | |
| CN104733719A (en) | Method for preparing germanium-based cathode material for lithium ion battery by adopting carbothermic reduction method | |
| CN103050692A (en) | Preparation method of grapheme-lithium manganese silicate anode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| DD01 | Delivery of document by public notice |
Addressee: Wan Taipeng Document name: Notification that Application Deemed to be Withdrawn |
|
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20141022 |