CN1937283A - Lithium ion cell cathode and its manufacturing method - Google Patents
Lithium ion cell cathode and its manufacturing method Download PDFInfo
- Publication number
- CN1937283A CN1937283A CNA200610016194XA CN200610016194A CN1937283A CN 1937283 A CN1937283 A CN 1937283A CN A200610016194X A CNA200610016194X A CN A200610016194XA CN 200610016194 A CN200610016194 A CN 200610016194A CN 1937283 A CN1937283 A CN 1937283A
- Authority
- CN
- China
- Prior art keywords
- additive
- lithium
- nitrogen compound
- battery
- metal oxide
- 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
- Secondary Cells (AREA)
Abstract
The cathode materials include all carbon material and conduction agents capable of reversible absorbing and discharging lithium. Characters are that additive substances are added to cathode material of carbon; additive substances are composed of one or many of metallic oxides and/or nitrogen compound of lithium; the said metallic oxides are Fe2O3, Fe3O4, FeO, Li4/3Ti5/4O4, NiO etc; general expression of nitrogen compound of lithium is as Li3-xMxN, where M as one or multiple metal elements: Co, Ni, Cu, Mg, Fe; level of addition of additive substances is 0.01%-8% of gross weight of active substances. Potential of putting lithium off for two kinds of additive substances is higher than the said potential of carbon material obviously. Thus, the invention solves issues of ascending potential of electrode, and preventing ballooning of battery when batteries are stored at discharging state so as to retain high charging and discharging efficiency, and good cycle performance.
Description
Technical field
The present invention relates to a kind of lithium ion battery and preparation method thereof, particularly a kind of lithium ion battery negative and preparation method thereof.
Background technology
Superior functions such as at present, average output voltage height, specific energy are big because lithium ion battery has, discharging voltage balance, safe and long working life; Therefore, can be used as the power supply of mobile electronic products such as mobile phone, notebook computer, field camera, camera, can also be as the power supply of DVD and electric bicycle, its application is boundless.
Employed negative plate is that various material with carbon elements are made in the existing lithium ion battery.Material with carbon element has the efficiency for charge-discharge height, the advantage of good cycle.But with the material with carbon element be the battery of negative pole when storing under discharge condition, electrolyte can take place to decompose and produce gas at negative pole, cause the bulging of battery.In order to address this problem, Chinese patent CN 1393947A proposes to add metals such as Si, Sn, Ge, Mg, Ca, Al, Pb, In, Co, Ag, Pt in negative pole.Though the suction that these metals can be reversible, put lithium,, its starting efficiency is low, and in cyclic process, volumetric expansion is big, self efflorescence, cycle performance is relatively poor; And, cause the cycle performance deterioration because the volume excessive expansion also can cause coming off of carbon negative pole.
Summary of the invention
The objective of the invention is to overcome above-mentioned weak point, a kind of lithium ion battery negative and preparation method thereof is provided; Under discharge condition, preserve the reaction that battery can effectively suppress negative pole and electrolyte, prevent the battery bulging, keep higher efficiency for charge-discharge and excellent cycle performance simultaneously.
The technical solution adopted in the present invention is for achieving the above object:
A kind of lithium ion battery negative, the negative material that is adopted comprise all reversible suctions, the material with carbon element of putting lithium and conductive agent; It is characterized in that adding in carbon negative pole material additive, additive is one or more compositions of metal oxide and/or lithium nitrogen compound; Described metal oxide is Fe
2O
3, Fe
3O
4, FeO, Li
4/3Ti
5/4O
4, NiO, Co
3O
4, MnO
2, CaO, CoO, Co
2O
3Lithium nitrogen compound general formula is: Li
3-xM
xN, wherein M is one or more metallic elements, as Co, Ni, Cu, Mg, Fe; The addition of additive is 0.01%～8% of an active material gross weight.
The concrete implementation step of the manufacture method of lithium ion battery negative is as follows: at first, Kynoar is dissolved in the N-methyl pyrrolidone routinely, make glue, then with material with carbon element and described metal oxide or/and the mixed-powder of one or more in the lithium nitrogen compound and conductive agent add in the above-mentioned glue, mixing is made slurry; Described metal oxide is or/and the addition of lithium nitrogen compound is 0.01%～8% of an active material gross weight; Slurry is coated on the Copper Foil uniformly, after temperature under the vacuum is 70～130 ℃ of oven dry, rolls and make negative plate.
The lithium ion battery that the present invention relates to, its positive pole, electrolyte and barrier film are that common process is made.As: positive pole can be all reversible suctions, puts the transition metal oxide that contains lithium of lithium, as LiCoO
2, LiMn
2O
4, LiMnO
2, LiNiO
2, LiNi
0.8Co
0.2O
2, LiNi
1/3Co
1/3Mn
1/3O
2Electrolyte is made up of solvent and the electrolytic salt that is dissolved in the solvent.Electrolytic salt can adopt LiPF
6, LiAsF
6, LiClO
4, LiBF
4, LiCF
3SO
3, LiN (CF
3SO
2)
2, LiN (C
2F
5SO
2)
2In one or more.The solvent that electrolyte adopted is ester class, ethers, as ethylene carbonate, propene carbonate, butylene, vinylene carbonate, carbonic acid first propyl ester, ethyl propyl carbonic acid ester, dimethyl carbonate, diethyl carbonate, Methylethyl carbonic ester, ethyl acetate, 1,2-dimethoxy-ethane, oxolane.The main distinction of the present invention and existing lithium ion battery is that the negative pole that adopts is the negative pole of the invention described above.
Beneficial effect of the present invention:, therefore after charging for the first time, no longer participate in follow-up charge and discharge cycles, thereby can not influence the cycle performance of battery because metal oxide takes off lithium current potential height; And nitride originally itself just can take off lithium under the situation of not inserting lithium, thereby its adding can improve the efficiency for charge-discharge of battery.And the lithium current potential that takes off of two class additives all is higher than material with carbon element, therefore the common adding of this two classes additive can be when effectively solving under the discharge condition storage battery electrode potential rise and the bulging problem in, keep higher efficiency for charge-discharge and excellent cycle performance.
Embodiment
Below in conjunction with preferred embodiment, to details are as follows according to embodiment provided by the invention:
Embodiment 1
Anodal making: Kynoar (PVDF) is dissolved in the N-methyl pyrrolidone (NMP), makes glue, then with LiCoO
2Add in the above-mentioned glue with the mixed-powder of acetylene black, mixing is made slurry, wherein LiCoO
2: acetylene black: PVDF=93: 3: 4.Then slurry is coated on the aluminium foil of 20 μ m uniformly, after the following 100 ℃ of oven dry of vacuum, is rolled into the positive plate of 140 μ m.
The making of negative pole: at first, routinely Kynoar (PVDF) is dissolved in the N-methyl pyrrolidone (NMP), as makes the glue of 12% (quality percentage composition); Then with material with carbon element as: carbonaceous mesophase spherules (MCMB), native graphite, Delanium, cracking carbon, carbon fiber, carbon nano-tube and as described in the mixed-powder of additive and conductive agent such as SP, acetylene black add in the above-mentioned glue; Described additive is one or more compositions in metal oxide and/or the lithium nitrogen compound; Described metal oxide is Fe
2O
3, Fe
3O
4, FeO, Li
4/3Ti
5/4O
4, NiO, Co
3O
4, MnO
2, CaO, CoO, Co
2O
3Lithium nitrogen compound general formula is: Li
3-xM
xN, wherein M is one or more metallic elements, as Co, Ni, Cu, Mg, Fe; The addition of additive is 0.01%～8% of an active material gross weight.As: with MCMB and Fe
2O
3And Li
2.6Co
0.4(MCMB: additive=98: 2, additive are Fe to the mixed-powder of N
2O
3: Li
2.6Co
0.4N=50: 50) and conductive agent SP add in the above-mentioned glue, mixing is made slurry, wherein (MCMB+ additive): SP: PVDF=94: 2: 4; Slurry is coated on the 10 μ m Copper Foils uniformly, after temperature under the vacuum is 70～130 ℃ of oven dry, rolls the negative plate of making 150 μ m.
The preparation of electrolyte:
Routinely with EC and DEC mixed, then with LiPF with 1: 1
6Be dissolved in wherein, make the electrolyte that concentration is 1mol/L.
The making of battery:
Routinely above-mentioned positive and negative plate is wound into the utmost point group of 053048 model with the thick polypropylene micro-pore septum of 20 μ m, uses the plastic-aluminum shell to encapsulate and inject electrolyte.
Embodiment 2
Other implementation step is with reference to embodiment 1, and just additive is MnO
2: Li
2.6Co
0.4N=50: 50, the addition of additive is 2% of an active material gross weight.
Embodiment 3
Other implementation step is with reference to embodiment 1, and just additive is Co
2O
3: Li
2.6Co
0.4N=50: 50, the addition of additive is 2% of an active material gross weight.
Embodiment 4
Other implementation step is with reference to embodiment 1, and just additive is Li
4/3Ti
5/4O
4: Li
2.6Co
0.4N=50: 50, the addition of additive is 2% of an active material gross weight.
Embodiment 5
Other implementation step is with reference to embodiment 1, and just additive is NiO: Li
2.6Co
0.4N=50: 50, the addition of additive is 2% of an active material gross weight.
Embodiment 6
Other implementation step is with reference to embodiment 1, and just additive is Fe
2O
3: Li
2.6Fe
0.4N=50: 50, the addition of additive is 2% of an active material gross weight.
Embodiment 7
Other implementation step is with reference to embodiment 1, and just additive is Fe
2O
3: Li
2.6Cu
0.4N=50: 50, the addition of additive is 2% of an active material gross weight.
Embodiment 8
Other implementation step is with reference to embodiment 1, and just additive is Fe
2O
3: Li
2.6Co
0.4N=0: 100, the addition of additive is 2% of an active material gross weight.
Embodiment 9
Other implementation step is with reference to embodiment 1, and just additive is Fe
2O
3: Li
2.6Co
0.4N=20: 80, the addition of additive is 2% of an active material gross weight.
Embodiment 10
Other implementation step is with reference to embodiment 1, and just additive is Fe
2O
3: Li
2.6Co
0.4N=80: 20, the addition of additive is 2% of an active material gross weight.
Embodiment 11
Other implementation step is with reference to embodiment 1, and just additive is Fe
2O
3: Li
2.6Co
0.4N=100: 0, the addition of additive is 2% of an active material gross weight.
Embodiment 12
Other implementation step and additive are with reference to embodiment 9, and just the addition of additive is 0.01% of an active material gross weight.
Embodiment 13
Other implementation step and additive are with reference to embodiment 9, and just the addition of additive is 5% of an active material gross weight.
Embodiment 14
Other implementation step and additive are with reference to embodiment 9, and just the addition of additive is 8% of an active material gross weight.
Comparative example 1
Other implementation step and additive be with reference to embodiment 9, and just the addition of additive is 9% of an active material gross weight, exceeds the framework of the present definition, as comparative example of the present invention with reference to contrast.
Comparative example 2
Do not add substance of the present invention in the carbon material used as anode, as comparative example of the present invention with reference to contrast.
The battery behavior test is as follows:
The battery that said method is made with the 100mA constant current charge to 4.2V, then under 4.2V voltage constant voltage charge to electric current less than 30mA; Again with the 1000mA constant-current discharge to 2.2V.Measure the initial capacity of battery, be designated as Q
1
The battery of making according to the method for each embodiment and comparative example respectively is divided into 2 groups, and one group is carried out cyclic test, and another group is stored test.
Wherein, cyclic test is carried out as follows, battery with the 1C constant current charge to 4.2V, and under 4.2V voltage constant voltage charge to electric current less than 30mA; Battery, circulates 400 times to 2.5V with the 1C constant-current discharge then, and the discharge capacity of the 400th circulation is designated as Q
400Capability retention is R (%)=(Q
1/ Q
400) * 100.
The storage experimental technique is: after 60 ℃ of constant temperature stored for 2 weeks, and the measuring voltage value, and observe whether the generation of bulging phenomenon is arranged.
Experiment comparing result such as table 1:
Table 1
| Embodiment | Additive kind in the negative pole | Two kinds of additive quality ratios | The content (quality %) of additive in active material | Initial charge capacity (mAh) | Initial discharge capacity (mAh) | Starting efficiency (%) | 400 circulation back capacity (mAh) | 400 circulation back capability retentions (%) | Cell voltage (V) after 60 ℃ of 2 weeks of constant temperature storage | Whether battery bulging | |
| Metal oxide | The lithium nitrogen compound | ||||||||||
| 1 | Fe 2O 3 | Li 2.6Co 0.4N | 50∶50 | 2 | 1057 | 959 | 90.7 | 787 | 82.1 | 2.4 | Not |
| 2 | MnO 2 | 1056 | 957 | 90.6 | 785 | 82.0 | 2.4 | Not | |||
| 3 | Co 2O 3 | 1060 | 961 | 90.7 | 789 | 82.1 | 2.4 | Not | |||
| 4 | Li 4/3Ti 5/4O 4 | 1053 | 957 | 90.9 | 786 | 82.2 | 2.4 | Not | |||
| 5 | NiO | 1059 | 958 | 90.5 | 785 | 82.0 | 2.4 | Not | |||
| 1 | Fe 2O 3 | Li 2.6Co 0.4N | 50∶50 | 2 | 1057 | 959 | 90.7 | 787 | 82.1 | 2.4 | Not |
| 6 | Li 2.6Fe 0.4N | 1065 | 968 | 90.9 | 796 | 82.2 | 2.4 | Not | |||
| 7 | Li 2.6Cu 0.4N | 1045 | 947 | 90.6 | 776 | 81.9 | 2.4 | Not | |||
| 8 | Fe 2O 3 | Li 2.6Co 0.4N | 0∶100 | 2 | 1052 | 973 | 92.5 | 798 | 82.0 | 2.4 | Not |
| 9 | 20∶80 | 1055 | 962 | 91.2 | 789 | 82.0 | 2.4 | Not | |||
| 1 | 50∶50 | 1057 | 959 | 90.7 | 787 | 82.1 | 2.4 | Not | |||
| 10 | 80∶20 | 1062 | 959 | 90.3 | 789 | 82.3 | 2.3 | Not | |||
| 11 | 100∶0 | 1067 | 953 | 89.3 | 782 | 82.1 | 2.1 | Not | |||
| 12 | Fe 2O 3 | Li 2.6Co 0.4N | 20∶80 | 0.01 | 1049 | 962 | 91.7 | 794 | 82.5 | 2.2 | Not |
| 1 | 2 | 1055 | 962 | 91.2 | 789 | 82.0 | 2.4 | Not | |||
| 13 | 5 | 1075 | 977 | 90.9 | 798 | 81.7 | 2.4 | Not | |||
| 14 | 8 | 1109 | 1002 | 90.4 | 812 | 81.0 | 2.4 | Not | |||
| Comparative example 1 | Fe 2O 3 | Li 2.6Co 0.4N | 20∶80 | 9 | 1124 | 1006 | 89.5 | 800 | 79.5 | 2.4 | Not |
| Comparative example 2 | 1034 | 951 | 92.0 | 791 | 83.1 | 0.8 | Be | ||||
As can be seen from Table 1:
(1) different metal oxides and Li have been enumerated respectively in the table
2.6Co
0.4N mixes, Fe
2O
3Mix with different lithium nitrogen compounds, join the effect in the carbon material used as anode then, that the first charge-discharge efficiency of battery descends and not obvious, and after 400 charge and discharge cycles, the battery capacity conservation rate is compared with the battery that does not add additive and is not had too big variation, illustrates that the cycle performance of battery keeps good.The battery that adds additive in the negative pole is after 60 ℃ of overdischarge attitudes stored for 2 weeks, and cell voltage descends not obvious, effectively suppressed the rising of negative electrode current potential, and the situation of bulging does not appear in battery.And the battery that does not add additive in the comparative example 2 in the negative pole is through the overdischarge attitude after 60 ℃ of 2 weeks of storage, and cell voltage drops to 0.8V, and battery generation bulging.One or more different metal oxides also can be obtained same effect with after one or more lithium nitrogen compounds mix.
(2) shown and in carbon material used as anode, added Fe in the table
2O
3With Li
2.6Co
0.4The mixture of N, (Fe
2O
3With Li
2.6Co
0.4The mass ratio difference of N) experiment effect after.The result shows when being used alone or using simultaneously two kinds of additives, be not subjected under the situation of big influence at the efficiency for charge-discharge and the cycle performance that guarantee battery equally, after 60 ℃ of overdischarge attitudes stored for 2 weeks, cell voltage descended not obvious, and the situation of bulging does not appear in battery.The mass ratio of metal oxide and lithium nitrogen compound all can be obtained above-mentioned effect at 0: 100～100: 0 o'clock.
(3) shown in carbon material used as anode in the table that adding mass percent is behind 0.01%～8% the additive, also to have obtained above-mentioned effect.But when the content of additive surpasses 8%, reach 9% as comparative example 1, though obviously do not rise through the voltage of storage back battery, bulging does not take place in battery yet, it is more that but its cycle efficieny and the back capability retention that circulates for 400 times all descend, the obvious variation of cycle performance.
Therefore, an amount of adding of additive can effectively suppress the rising of negative pole current potential, the generation of battery bulging when depositing battery under the attitude that prevents to discharge; Keep higher efficiency for charge-discharge and excellent cycle performance simultaneously.
Above-mentioned detailed description of lithium ion battery negative and preparation method thereof being carried out with reference to embodiment; be illustrative rather than determinate; can exemplify out several embodiment according to institute's limited range; therefore in the variation and the modification that do not break away under the general plotting of the present invention, should belong within protection scope of the present invention.
Claims (2)
1, a kind of lithium ion battery negative, the negative material that is adopted comprises all reversible suctions, the material with carbon element of putting lithium and conductive agent; It is characterized in that adding in carbon negative pole material additive, additive is one or more compositions of metal oxide and/or lithium nitrogen compound; Described metal oxide is Fe
2O
3, Fe
3O
4, FeO, Li
4/3Ti
5/4O
4, NiO, Co
3O
4, MnO
2, CaO, CoO, Co
2O
3Lithium nitrogen compound general formula is: Li
3-xM
xN, wherein M is one or more metallic elements, as Co, Ni, Cu, Mg, Fe; The addition of additive is 0.01%～8% of an active material gross weight.
2, the manufacture method of lithium ion battery negative according to claim 1, it is characterized in that implementation step is as follows: at first, Kynoar is dissolved in the N-methyl pyrrolidone routinely, make glue, then with material with carbon element and described metal oxide or/and the mixed-powder of one or more in the lithium nitrogen compound and conductive agent add in the above-mentioned glue, mixing is made slurry; Described metal oxide is or/and the addition of lithium nitrogen compound is 0.01%～8% of an active material gross weight; Slurry is coated on the Copper Foil uniformly, after temperature under the vacuum is 70～130 ℃ of oven dry, rolls and make negative plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200610016194XA CN1937283A (en) | 2006-10-20 | 2006-10-20 | Lithium ion cell cathode and its manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200610016194XA CN1937283A (en) | 2006-10-20 | 2006-10-20 | Lithium ion cell cathode and its manufacturing method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1937283A true CN1937283A (en) | 2007-03-28 |
Family
ID=37954658
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA200610016194XA Pending CN1937283A (en) | 2006-10-20 | 2006-10-20 | Lithium ion cell cathode and its manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1937283A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009103202A1 (en) * | 2008-02-22 | 2009-08-27 | Byd Company Limited | Negative electrode for battery and lithium battery using the same |
-
2006
- 2006-10-20 CN CNA200610016194XA patent/CN1937283A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009103202A1 (en) * | 2008-02-22 | 2009-08-27 | Byd Company Limited | Negative electrode for battery and lithium battery using the same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110112465B (en) | Electrolyte for battery with lithium-rich manganese-based positive electrode material system and lithium ion battery | |
| CN101202362B (en) | Rechargeable lithium battery | |
| KR102103898B1 (en) | Additive for nonaqueous electrolyte, nonaqueous electrolyte for lithium secondary battery comprising the same, and lithium secondary battery | |
| CN102637903A (en) | Formation method of lithium ion battery | |
| CN102569722A (en) | Lithium ion secondary battery and anode thereof | |
| CN102394311A (en) | Lithium ion secondary battery with high energy density | |
| CN102723459A (en) | Lithium-ion secondary battery and positive plate thereof | |
| CN102738511A (en) | Lithium ion battery and electrolyte thereof | |
| CN101183711A (en) | Non-aqueous electrolyte secondary cell | |
| CN109888384B (en) | Electrolyte and battery containing the same | |
| CN112956063B (en) | Electrolyte and electrochemical device and electronic device including the same | |
| JP2006216509A (en) | Positive electrode and nonaqueous electrolyte secondary battery using the same | |
| CN109309227A (en) | Lithium ion battery and positive electrode active material thereof | |
| CN107579280A (en) | The lithium secondary cell electrolyte and lithium secondary battery of the ester of silicon substrate containing cyclic disulfonic acid | |
| CN111200164A (en) | Lithium ion battery electrolyte and lithium ion battery | |
| CN108390098B (en) | High-voltage lithium ion battery electrolyte and high-voltage lithium ion battery | |
| CN103515651A (en) | High voltage carbonic ester base electrolyte of lithium ion battery as well as preparation method and application thereof | |
| CN115763975A (en) | Electrolyte and lithium ion battery | |
| JP2008235150A (en) | Non-aqueous electrolyte secondary battery | |
| CN114583282A (en) | Multifunctional electrolyte for absorbing and supplementing lithium agent and decomposing gas and application thereof | |
| CN109659617A (en) | Lithium ion secondary battery and its electrolyte | |
| CN1558464A (en) | Lithium ion battery electrolyte containing organophosphorus compounds and battery formed thereby | |
| WO2023241147A1 (en) | Electrolyte and battery containing said electrolyte | |
| CN112310478B (en) | Electrolyte and electrochemical device thereof | |
| CN112467218B (en) | Lithium metal battery based on copper nitrate electrolyte additive |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |