CN103000903B

CN103000903B - Precursor doped with carbon nanomaterial and preparation method thereof as well as spherical lithium metal oxide anode material and preparation method thereof

Info

Publication number: CN103000903B
Application number: CN201210494738.9A
Authority: CN
Inventors: 杜春雨; 盛夏; 陈猛; 尹鸽平; 左朋建; 程新群; 马玉林
Original assignee: Harbin Institute of Technology
Current assignee: Harbin Institute of Technology
Priority date: 2012-11-28
Filing date: 2012-11-28
Publication date: 2015-01-28
Anticipated expiration: 2032-11-28
Also published as: CN103000903A

Abstract

The invention discloses a precursor doped with a carbon nanomaterial and a preparation method thereof as well as a spherical lithium metal oxide anode material and a preparation method thereof, and relates to the precursor and the preparation method thereof as well as the lithium metal oxide anode material and the preparation method thereof. The invention aims at solving the problems of great initial irreversible capacity loss, poor rate capability and low tap density of the existing lithium metal oxide anode material due to the fact that the precursor for perfecting the lithium metal oxide anode material cannot be prepared by the prior art. The precursor is the metal oxide anode or metal carbonate doped with the carbon nanomaterial. The method comprises the steps of firstly preparing a metal ion material, orderly preparing mixed metal ion salt solution, a precipitator, a complexing agent, and carbon nanomaterial suspension liquid, then carrying out co-precipitation reaction, and carrying out washing and drying treatment. The spherical lithium metal oxide anode material is prepared from lithium compound and the precursor doped with the carbon nanomaterial. The method comprises the steps of firstly, processing the precursor in advance, mixing with lithium and then sintering.

Description

A kind of presoma of doping carbon nano material and preparation method and spherical lithium metal oxide positive electrode and preparation method

Technical field

The present invention relates to a kind of presoma and preparation method and lithium metal oxide positive electrode and preparation method.

Background technology

Lithium ion battery because voltage platform is high, large, the memory-less effect of energy density, the advantage such as have extended cycle life, become the substitute of the batteries such as ni-mh, NI-G, plumbic acid gradually, and be widely used in the multiple fields such as daily life, industry, military affairs.Positive electrode is the key factor determining the performances such as lithium ion battery energy density, useful life and fail safe.The anode material for lithium-ion batteries of batch application mainly contains cobalt acid lithium, LiMn2O4, LiFePO4 etc. in the market.The structure comparison of cobalt acid lithium is stablized, and is a kind of very ripe positive electrode, occupies the leading position of positive electrode at present, but it is its resource-constrained, expensive, there is problem of environmental pollution, and its useful life is shorter, fail safe is very poor, development is restricted.LiMn2O4 has the advantages such as aboundresources, low price, fail safe are good, but its cyclical stability is poor, bad with electrolyte compatible.LiFePO 4 material has the advantages such as nontoxic, pollution-free, security performance is good, raw material sources is extensive, the life-span is long, but its tap density is lower, poorly conductive, lithium ion diffusion velocity are slow.And, the theoretical capacity of this different materials is not very high, its actual capacity is also many lower than 150mAh/g, which greatly limits the energy density of lithium ion battery, thus constrains the application of lithium ion battery in the field such as portable electric appts and electric automobile.

Possess the embedding oxidate for lithium Li of polynary transition metal such as capacity is high, the nickel cobalt manganese of the multiple advantage such as good cycling stability and low cost in recent years _1+xmn _αco _βni _γm _yo ₂(wherein M is one or more in Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb, Sc, and alpha+beta+γ+y=1,0 < α≤1,0≤β≤1,0≤γ≤1,0≤x≤0.34,0≤y≤0.5 is zero when β with γ is different) just attracting the extensive concern of Chinese scholars and research and development institution.The embedding oxidate for lithium Li of polynary transition metal such as nickel cobalt manganese _1+xmn _αco _βni _γm _yo ₂during middle x=0, be three common metaclass materials.This material is due to the cooperative effect between transition metal, and chemical property is better than arbitrary one-component oxide.Calendar year 2001 OhZuku and Makimura has synthesized the trielement composite material LiNi of Ni:Co:Mn=1:1:1 first _1/3co _1/3mn _1/3o ₂, Canadian Dahn etc. have studied change of component to LiMn simultaneously _αco _βni _γo ₂the impact of trielement composite material crystal structure, capacity, high rate performance and thermal stability.There is obvious trielement synergistic effect in such material: introduces Co element, effectively can reduce lithium nickel ion mixing phenomenon, the layer structure of stabilizing material; Introduce Ni element, the specific capacity of material can be significantly improved; Introduce Mn element, not only can reduce costs, but also the fail safe stability of material can be improved.In addition, the research metals such as a small amount of Al, Ti that show to adulterate can improve the performances such as the multiplying power of the embedding oxidate for lithium material of polynary transition metal and cycle life further.

As embedding oxidate for lithium Li of polynary transition metal such as above-mentioned nickel cobalt manganese _1+xmn _αco _βni _γm _yo ₂during middle x > 0, be also referred to as rich lithium material, this molecular formula also can be rewritten as xLi ₂mnO ₃(1-x) LiM _ao ₂, wherein LiM _ao ₂the embedding oxidate for lithium LiMn of transition metal _{α `}co _{β `}ni _{γ `}o ₂one or more in (0 < α `≤1,0≤β `≤1,0≤γ `≤1, β `+ γ `>=0) or its metal-doped materials.Rich lithium material is the class positive electrode that the researcher of Argonne National Laboratory of USDOE develops, and this material list reveals very high specific capacity, more than 250mAh/g, close to 2 times of conventional lithium ion battery positive electrode capacity.And, the cost of lithium ion battery greatly can be reduced with the cobalt of manganese base lithium-rich anode material fictitious hosts costliness, nickel.In addition, rich lithium material also has the advantages such as the higher and production technology of fail safe is simple.Therefore, rich lithium material is a kind of positive electrode had a extensive future, adopt the lithium ion battery of rich lithium material will obtain extensive use in a series of field, comprise the consumption electronic product such as mobile phone, notebook computer, wireless tool and the medical apparatus such as cardiac pacemaker, defibrillator, and electric automobile and hybrid vehicle etc.

But, be that the embedding oxidate for lithium of polynary transition metal or rich lithium material all exist the problems such as irreversible capacity loss is comparatively large, high rate performance is poor first.And compared with the business cobalt acid lithium material of maturation, also there is the lower problem of tap density in this two classes material.These problems seriously hinder the practicalization of the embedding oxidate for lithium of polynary transition metal and rich lithium material.Therefore, prior art cannot prepare the presoma improving the embedding oxidate for lithium of polynary transition metal and rich lithium material performance, and the embedding oxidate for lithium of polynary transition metal causing existing method to be prepared or rich lithium material exist the problem that irreversible capacity loss is comparatively large, high rate performance is poor and tap density is lower first.

Summary of the invention

The object of the invention is to solve prior art and cannot prepare the presoma improving lithium metal oxide positive electrode, cause existing lithium metal oxide positive electrode to there is the problem that irreversible capacity loss is comparatively large, high rate performance is poor and tap density is lower first; And a kind of presoma of doping carbon nano material and preparation method and spherical lithium metal oxide positive electrode and preparation method are provided.

A kind of presoma of doping carbon nano material is Uniform Doped carbon nanomaterial, molecular formula is Mn _αco _βni _γm _y(OH) ₂metal hydroxides or Uniform Doped carbon nanomaterial, molecular formula be Mn _αco _βni _γm _ycO ₃metal carbonate; Wherein said Mn _αco _βni _γm _y(OH) ₂in 0 < α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ > 0, described Mn _αco _βni _γm _y(OH) ₂middle M is the one or wherein several in Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and Sc; Wherein said Mn _αco _βni _γm _ycO ₃in 0 < α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ > 0, described Mn _αco _βni _γm _ycO ₃middle M is the one or wherein several in Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and Sc.

A preparation method for the presoma of doping carbon nano material, specifically completes according to the following steps: one, prepare raw material: according to chemical formula Mn _αco _βni _γm _y(OH) ₂by Mn element: Co element: Ni element: M element mol ratio is α: β: γ: y preparation soluble manganese salt, soluble cobalt, soluble nickel salt and soluble M salt; Two, prepare hybrid metal ion salt solution: soluble manganese salt step one prepared, soluble cobalt, soluble nickel salt and soluble M salt join in solvent and mixes, be configured to the hybrid metal ion salt solution that hybrid metal ion concentration is 0.01mol/L ~ 5mol/L; Three, precipitation reagent is prepared: added by soluble hydroxide in solvent, be configured to OH ^-concentration is 0.1mol/L ~ 10mol/L precipitation reagent; Four, complexing agent is prepared: add in solvent by solubility ammonium salt or ammoniacal liquor, be configured to NH ₄ ⁺concentration is 0.1mol/L ~ 10mol/L complexing agent; Five, prepare carbon nanomaterial suspension: carbon nanomaterial is scattered in solvent, be configured to the carbon nanomaterial suspension that carbon nanomaterial concentration is 0.1mg/L ~ 50g/L; Six, coprecipitation reaction: the OH that hybrid metal ion concentration step 2 prepared is the hybrid metal ion salt solution of 0.01mol/L ~ 5mol/L, prepared by step 3 ^-the NH that concentration is 0.1mol/L ~ 10mol/L precipitation reagent, prepared by step 4 ₄ ⁺the carbon nanomaterial suspension of concentration to be carbon nanomaterial concentration prepared by 0.1mol/L ~ 10mol/L complexing agent and step 5 be 0.1mg/L ~ 50g/L adds in the reactor that reaction initial soln is housed simultaneously, hybrid metal ion concentration prepared by step 2 is the speed that adds of the hybrid metal ion salt solution of 0.01mol/L ~ 5mol/L is 0.1mL/min ~ 1000mL/min, OH prepared by step 3 ^-concentration is the speed that adds of 0.1mol/L ~ 10mol/L precipitation reagent is 0.1mL/min ~ 1000mL/min, NH prepared by step 4 ₄ ⁺concentration is the speed that adds of 0.1mol/L ~ 10mol/L complexing agent is 0.1mL/min ~ 1000mL/min, carbon nanomaterial concentration prepared by step 5 is the speed that adds of the carbon nanomaterial suspension of 0.1mg/L ~ 50g/L is 0.1mL/min ~ 500mL/min, and temperature be 20 DEG C ~ 90 DEG C, mixing speed to be 100rpm ~ 10000rpm, pH be 5 ~ 13 and inert gas shielding under react, namely obtain spherical precipitation thing; Seven, the dry process of washing: the spherical precipitation thing first adopting washed with de-ionized water step 6 to obtain, the pH cleaned to filtrate is neutrality, is then 20 DEG C ~ 150 DEG C in temperature and is dried to constant weight, namely obtain Uniform Doped carbon nanomaterial, molecular formula is Mn _αco _βni _γm _y(OH) ₂metal hydroxides; Described Mn described in step one _αco _βni _γm _y(OH) ₂in 0 < α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ > 0, wherein said Mn _αco _βni _γm _y(OH) ₂middle M is the one or wherein several in Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and Sc; The volume of the reaction initial soln described in step 6 and the volumetric ratio of reactor are (0.001 ~ 0.8): 1.

A preparation method for the presoma of doping carbon nano material, specifically completes according to the following steps: one, prepare raw material: according to chemical formula Mn _αco _βni _γm _ycO ₃by Mn element: Co element: Ni element: M element mol ratio is α: β: γ: y preparation soluble manganese salt, soluble cobalt, soluble nickel salt and soluble M salt; Two, prepare hybrid metal ion salt solution: soluble manganese salt step one prepared, soluble cobalt, soluble nickel salt and soluble M salt join in solvent and mixes, be configured to the hybrid metal ion salt solution that hybrid metal ion concentration is 0.01mol/L ~ 5mol/L; Three, precipitation reagent is prepared: added by soluble hydroxide in solvent, be configured to CO ₃ ^2-concentration is 0.1mol/L ~ 10mol/L precipitation reagent; Four, complexing agent is prepared: add in solvent by solubility ammonium salt or ammoniacal liquor, be configured to NH ₄ ⁺concentration is 0.1mol/L ~ 10mol/L complexing agent; Five, prepare carbon nanomaterial suspension: carbon nanomaterial is scattered in solvent, be configured to the carbon nanomaterial suspension that carbon nanomaterial concentration is 0.1mg/L ~ 50g/L; Six, coprecipitation reaction: the CO that hybrid metal ion concentration step 2 prepared is the hybrid metal ion salt solution of 0.01mol/L ~ 5mol/L, prepared by step 3 ₃ ^2-the NH that concentration is 0.1mol/L ~ 10mol/L precipitation reagent, prepared by step 4 ₄ ⁺the carbon nanomaterial suspension of concentration to be carbon nanomaterial concentration prepared by 0.1mol/L ~ 10mol/L complexing agent and step 5 be 0.1mg/L ~ 50g/L adds in the reactor that reaction initial soln is housed simultaneously, hybrid metal ion concentration prepared by step 2 is the speed that adds of the hybrid metal ion salt solution of 0.01mol/L ~ 5mol/L is 0.1mL/min ~ 1000mL/min, CO prepared by step 3 ₃ ^2-concentration is the speed that adds of 0.1mol/L ~ 10mol/L precipitation reagent is 0.1mL/min ~ 1000mL/min, NH prepared by step 4 ₄ ⁺concentration is the speed that adds of 0.1mol/L ~ 10mol/L complexing agent is 0.1mL/min ~ 1000mL/min, carbon nanomaterial concentration prepared by step 5 is the speed that adds of the carbon nanomaterial suspension of 0.1mg/L ~ 50g/L is 0.1mL/min ~ 500mL/min, and temperature be 20 DEG C ~ 90 DEG C, mixing speed to be 100rpm ~ 10000rpm, pH be 5 ~ 13 and inert gas shielding under react, namely obtain spherical precipitation thing; Seven, the dry process of washing: the spherical precipitation thing first adopting washed with de-ionized water step 6 to obtain, the pH cleaned to filtrate is neutrality, is then 20 DEG C ~ 150 DEG C in temperature and is dried to constant weight, namely obtain Uniform Doped carbon nanomaterial, molecular formula is Mn _αco _βni _γm _ycO ₃metal carbonate; Described Mn described in step one _αco _βni _γm _ycO ₃in 0 < α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ > 0, wherein said Mn _αco _βni _γm _ycO ₃middle M is the one or wherein several in Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and Sc; The volume of the reaction initial soln described in step 6 and the volumetric ratio of reactor are (0.001 ~ 0.8): 1.

A kind of spherical lithium metal oxide positive electrode is formed by the precursor power of lithium-containing compound and above-mentioned doping carbon nano material; In the presoma of described doping carbon nano material, the total amount of substance of metallic element is 1:(1 ~ 1.42 with the ratio of the amount of the Li elemental substance in described lithium-containing compound); The presoma of described doping carbon nano material is Uniform Doped carbon nanomaterial, molecular formula is Mn _αco _βni _γm _y(OH) ₂metal hydroxides or Uniform Doped carbon nanomaterial, molecular formula be Mn _αco _βni _γm _ycO ₃metal carbonate; Wherein said Mn _αco _βni _γm _y(OH) ₂in 0 < α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ > 0, described Mn _αco _βni _γm _y(OH) ₂middle M is the one or wherein several in Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and Sc; Wherein said Mn _αco _βni _γm _ycO ₃in 0 < α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ > 0, described Mn _αco _βni _γm _ycO ₃middle M is the one or wherein several in Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and Sc.

A kind of preparation method of spherical lithium metal oxide positive electrode, specifically complete according to the following steps: one, presoma preliminary treatment: by the presoma of doping carbon nano material according to claim 1 at 200 DEG C ~ 800 DEG C pre-burning 1h ~ 12h, obtain presoma after preliminary treatment; Two, mixed lithium sintering: mixed with lithium-containing compound by presoma after preliminary treatment, is then 600 DEG C ~ 1200 DEG C roasting 3h ~ 36h in temperature, cools to room temperature with the furnace and namely obtain spherical lithium metal oxide positive electrode; The presoma of the doping carbon nano material described in step one is Uniform Doped carbon nanomaterial, molecular formula is Mn _αco _βni _γm _y(OH) ₂metal hydroxides or Uniform Doped carbon nanomaterial, molecular formula be Mn _αco _βni _γm _ycO ₃metal carbonate; Wherein said Mn _αco _βni _γm _y(OH) ₂in 0 < α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, y is: 0≤y≤0.5, and alpha+beta+γ+y=1, β+γ > 0, described Mn _αco _βni _γm _y(OH) ₂middle M is the one or wherein several in Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and Sc; Wherein said Mn _αco _βni _γm _ycO ₃in 0 < α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, y is: 0≤y≤0.5, and alpha+beta+γ+y=1, β+γ > 0, described Mn _αco _βni _γm _ycO ₃middle M is the one or wherein several in Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and Sc; In the presoma of the doping carbon nano material described in step one, the total amount of substance of metallic element is 1:(1 ~ 1.42 with the ratio of the amount of the Li elemental substance in the lithium-containing compound described in step 2).

Advantage of the present invention: one, the presoma of doping carbon nano material prepared of the present invention can the uniformity of pyroreaction in acceleration of sintering process, thus the phenomenon suppressing oxygen in body phase lattice to deviate from room to a certain extent to be occupied by transition metal ions, promote the spherical lithium metal oxide positive electrode first charge-discharge efficiency prepared of the present invention, overcome the embedding oxidate for lithium of polynary transition metal prepared by existing method and rich lithium material exists the larger defect of irreversible capacity loss first; Two, the presoma of doping carbon nano material that prepared by the present invention can impel that material is inner forms 3D pore passage structure, there is 3D pore passage structure in the spherical lithium metal oxide positive electrode inside that therefore prepared by the present invention, facilitate the diffusion of lithium ion at material internal, improve the high rate performance of material; Three, the presoma of doping carbon nano material that prepared by the present invention can by the coring and increment process of the interpolation regulation and control presoma of carbon nanomaterial, and then in conjunction with the optimization of synthesis condition, the spheric granules that presoma pattern is homogeneous grain diameter can be controlled, the spherical lithium metal oxide positive electrode of high-tap density can be prepared thus; Four, the present invention prepares the method technique of the method for spherical lithium metal oxide positive electrode and the presoma of preparation doping carbon nano material simply, and preparation cost is low, and with short production cycle, and the spherical lithium metal oxide positive electrode (Li finally obtained _1+xmn _αco _βni _γm _yo ₂) steady quality, high power capacity, long circulation life and tap density is high.

Accompanying drawing explanation

Fig. 1 is the XRD collection of illustrative plates of the presoma of doping carbon nano material prepared by test one; Fig. 2 is the SEM figure that the presoma of doping carbon nano material prepared by test one amplifies 10000 times; Fig. 3 is that spherical lithium metal oxide positive electrode XRD prepared by test two schemes; Fig. 4 is the SEM figure that the spherical lithium metal oxide positive electrode of test two preparation amplifies 5000 times; Fig. 5 is charging and discharging curve figure, in figure, A represents spherical lithium metal oxide positive electrode charge graph prepared by test two, in figure, B represents spherical lithium metal oxide anode material discharging curve chart prepared by test two, in figure, C represents spherical lithium metal oxide positive electrode charge graph prepared by test two contrast test, and in figure, D represents spherical lithium metal oxide anode material discharging curve chart prepared by test two contrast test; Fig. 6 is high rate performance curve chart, and in figure, A represents the high rate performance curve chart of spherical lithium metal oxide positive electrode prepared by test two, and in figure, B represents the high rate performance curve chart of spherical lithium metal oxide positive electrode prepared by test two contrast test; Fig. 7 is the SEM figure that the presoma of doping carbon nano material prepared by test three amplifies 10000 times; Fig. 8 is that spherical lithium metal oxide positive electrode XRD prepared by test four schemes; Fig. 9 is the SEM figure that the spherical lithium metal oxide positive electrode of test four preparation amplifies 5000 times; Figure 10 is the SEM figure that the presoma of doping carbon nano material prepared by test five amplifies 5000 times.

Embodiment

Embodiment one: present embodiment is a kind of presoma of doping carbon nano material, the presoma of doping carbon nano material is Uniform Doped carbon nanomaterial, molecular formula is Mn _αco _βni _γm _y(OH) ₂metal hydroxides or Uniform Doped carbon nanomaterial, molecular formula be Mn _αco _βni _γm _ycO ₃metal carbonate.

Mn described in present embodiment _αco _βni _γm _y(OH) ₂in 0 < α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ > 0, described Mn _αco _βni _γm _y(OH) ₂middle M is the one or wherein several in Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and Sc.

Mn described in present embodiment _αco _βni _γm _ycO ₃in 0 < α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ > 0, described Mn _αco _βni _γm _ycO ₃middle M is the one or wherein several in Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and Sc.

Embodiment two: present embodiment is a kind of preparation method of presoma of doping carbon nano material, specifically completes according to the following steps: one, prepare raw material: according to chemical formula Mn _αco _βni _γm _y(OH) ₂by Mn element: Co element: Ni element: M element mol ratio is α: β: γ: y preparation soluble manganese salt, soluble cobalt, soluble nickel salt and soluble M salt; Two, prepare hybrid metal ion salt solution: soluble manganese salt step one prepared, soluble cobalt, soluble nickel salt and soluble M salt join in solvent and mixes, be configured to the hybrid metal ion salt solution that hybrid metal ion concentration is 0.01mol/L ~ 5mol/L; Three, precipitation reagent is prepared: added by soluble hydroxide in solvent, be configured to OH ^-concentration is 0.1mol/L ~ 10mol/L precipitation reagent; Four, complexing agent is prepared: add in solvent by solubility ammonium salt or ammoniacal liquor, be configured to NH ₄ ⁺concentration is 0.1mol/L ~ 10mol/L complexing agent; Five, prepare carbon nanomaterial suspension: carbon nanomaterial is scattered in solvent, be configured to the carbon nanomaterial suspension that carbon nanomaterial concentration is 0.1mg/L ~ 50g/L; Six, coprecipitation reaction: the OH that hybrid metal ion concentration step 2 prepared is the hybrid metal ion salt solution of 0.01mol/L ~ 5mol/L, prepared by step 3 ^-the NH that concentration is 0.1mol/L ~ 10mol/L precipitation reagent, prepared by step 4 ₄ ⁺the carbon nanomaterial suspension of concentration to be carbon nanomaterial concentration prepared by 0.1mol/L ~ 10mol/L complexing agent and step 5 be 0.1mg/L ~ 50g/L adds in the reactor that reaction initial soln is housed simultaneously, hybrid metal ion concentration prepared by step 2 is the speed that adds of the hybrid metal ion salt solution of 0.01mol/L ~ 5mol/L is 0.1mL/min ~ 1000mL/min, OH prepared by step 3 ^-concentration is the speed that adds of 0.1mol/L ~ 10mol/L precipitation reagent is 0.1mL/min ~ 1000mL/min, NH prepared by step 4 ₄ ⁺concentration is the speed that adds of 0.1mol/L ~ 10mol/L complexing agent is 0.1mL/min ~ 1000mL/min, carbon nanomaterial concentration prepared by step 5 is the speed that adds of the carbon nanomaterial suspension of 0.1mg/L ~ 50g/L is 0.1mL/min ~ 500mL/min, and temperature be 20 DEG C ~ 90 DEG C, mixing speed to be 100rpm ~ 10000rpm, pH be 5 ~ 13 and inert gas shielding under react, namely obtain spherical precipitation thing; Seven, the dry process of washing: the spherical precipitation thing first adopting washed with de-ionized water step 6 to obtain, the pH cleaned to filtrate is neutrality, is then 20 DEG C ~ 150 DEG C in temperature and is dried to constant weight, namely obtain Uniform Doped carbon nanomaterial, molecular formula is Mn _αco _βni _γm _y(OH) ₂metal hydroxides.

Described Mn described in present embodiment step one _αco _βni _γm _y(OH) ₂in 0 < α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ > 0, wherein said Mn _αco _βni _γm _y(OH) ₂middle M is the one or wherein several in Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and Sc.

The volume of the reaction initial soln described in present embodiment step 6 and the volumetric ratio of reactor are (0.001 ~ 0.8): 1.

When M described in present embodiment is complex element, be mixed by any ratio between each element.

The complexing agent that present embodiment step 4 obtains is except directly adding the reactor China and foreign countries that reaction initial soln is housed, precipitation reagent prepared by the hybrid metal ion salt solution also can prepared with step 2 in advance or step 3 mixes, carrying out the operation of step 6 again, is that 0.1mL/min ~ 1000mL/min adds in the reactor that reaction initial soln is housed with speed.Namely two kinds of materials that chemical reaction does not occur can be mixed in advance, then carry out the operation of step 6, be that 0.1mL/min ~ 1000mL/min adds in the reactor that reaction initial soln is housed with speed.

Except the carbon nanomaterial described in present embodiment step 5 is scattered in solvent, be configured to outside carbon nanomaterial suspension that carbon nanomaterial concentration is 0.1mg/L ~ 50g/L, carbon nanomaterial can also be scattered in hybrid metal ion salt solution prepared by step 2, one or wherein several in precipitation reagent prepared by step 3 and complexing agent prepared by step 4, in the suspension obtained after dispersion, carbon nanomaterial concentration is 0.1mg/L ~ 50g/L, the i.e. in advance hybrid metal ion salt solution prepared of carbon nanomaterial and step 2, one in precipitation reagent prepared by step 3 and complexing agent prepared by step 4 or wherein severally to mix, and then carry out the operation of step 6, be that 0.1mL/min ~ 1000mL/min adds in the reactor that reaction initial soln is housed with speed, first carbon nanomaterial can also be scattered in the reaction initial soln in reactor, in the carbon nanomaterial obtained after dispersion/reaction initial soln suspension, carbon nanomaterial concentration is 0.1mg/L ~ 50g/L, and then carry out the operation of step 6, be that 0.1mL/min ~ 1000mL/min adds in the reactor that carbon nanomaterial/reaction initial soln suspension is housed with speed, namely two kinds or two or more material that chemical reaction does not occur can be mixed in advance, then carry out the operation of step 6, be that 0.1mL/min ~ 1000mL/min adds in the reactor that reaction initial soln is housed with speed.

Embodiment three: the difference of present embodiment and embodiment two is: the soluble manganese salt described in step 2 is a kind of or wherein several mixture in manganese sulfate, manganese nitrate, manganese chloride, manganese sulfate hydrate, manganese nitrate hydrate and manganese chloride hydrate.Other are identical with embodiment two.

When soluble manganese salt described in present embodiment is mixture, be mixed by any ratio between each component.

Embodiment four: one of present embodiment and embodiment two or three difference is: the soluble cobalt described in step 2 is a kind of or wherein several mixture in cobaltous sulfate, cobalt nitrate, cobalt chloride, cobaltous sulfate hydrate, cobalt nitrate hydrate and cobalt chloride hydrate.Other are identical with embodiment two or three.

When soluble cobalt described in present embodiment is mixture, be mixed by any ratio between each component.

Embodiment five: one of present embodiment and embodiment two to four difference is: the soluble nickel salt described in step 2 is a kind of or wherein several mixture in nickelous sulfate, nickel nitrate, nickel chloride, nickel sulfate hydrate, nickel nitrate hydrate and nickel chloride hydrate.Other are identical with embodiment two to four.

When soluble nickel salt described in present embodiment is mixture, be mixed by any ratio between each component.

Embodiment six: one of present embodiment and embodiment two to five difference is: the soluble M salt described in step 2 is a kind of or wherein several mixture in sulfuric acid M, nitric acid M, chlorination M, sulfuric acid M hydrate, nitric acid M hydrate and chlorination M hydrate.Other are identical with embodiment two to five.

When soluble M salt described in present embodiment is mixture, be mixed by any ratio between each component.

Embodiment seven: one of present embodiment and embodiment two to six difference is: the solvent described in step 2 is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, the methanol/ethanol aqueous solution, the methanol/acetone aqueous solution, the ethanol/acetone aqueous solution or methanol/ethanol/aqueous acetone solution.Other are identical with embodiment two to six.

Methanol aqueous solution described in present embodiment is mixed by any ratio by methyl alcohol and deionized water and forms.

Ethanol water described in present embodiment is mixed by any ratio by ethanol and deionized water and forms.

Aqueous acetone solution described in present embodiment is mixed by any ratio by acetone and deionized water and forms.

The methanol/ethanol aqueous solution described in present embodiment is mixed by any ratio by methyl alcohol, ethanol and deionized water and forms.

The methanol/acetone aqueous solution described in present embodiment is mixed by any ratio by methyl alcohol, acetone and deionized water and forms.

The ethanol/acetone aqueous solution described in present embodiment is mixed by any ratio by ethanol, acetone and deionized water and forms.

Methanol/ethanol/aqueous acetone solution described in present embodiment is mixed by any ratio by methyl alcohol, ethanol, acetone and deionized water and forms.

Embodiment eight: one of present embodiment and embodiment two to seven difference is: the solvent described in step 3 is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, the methanol/ethanol aqueous solution, the methanol/acetone aqueous solution, the ethanol/acetone aqueous solution or methanol/ethanol/aqueous acetone solution.Other are identical with embodiment two to seven.

Embodiment nine: one of present embodiment and embodiment two to eight difference is: the soluble hydroxide described in step 3 is a kind of or wherein several mixture in NaOH, potassium hydroxide, lithium hydroxide and barium hydroxide.Other are identical with embodiment two to eight.

When soluble hydroxide described in present embodiment is mixture, be mixed by any ratio between each component.

Embodiment ten: one of present embodiment and embodiment two to nine difference is: the solubility ammonium salt described in step 4 is a kind of or wherein several mixture in carbonic hydroammonium, ammonium carbonate, ammonium sulfate, ammonium hydrogen sulfate, ammonium chloride, ammonium phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate.Other are identical with embodiment two to nine.

When solubility ammonium salt described in present embodiment is mixture, be mixed by any ratio between each component.

Embodiment 11: one of present embodiment and embodiment two to ten difference is: the solvent described in step 4 is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, the methanol/ethanol aqueous solution, the methanol/acetone aqueous solution, the ethanol/acetone aqueous solution or methanol/ethanol/aqueous acetone solution.Other are identical with embodiment two to ten.

Embodiment 12: one of present embodiment and embodiment two to ten one difference is: the solvent described in step 5 is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, the methanol/ethanol aqueous solution, the methanol/acetone aqueous solution, the ethanol/acetone aqueous solution or methanol/ethanol/aqueous acetone solution.Other are identical with embodiment two to ten one.

Embodiment 13: one of present embodiment and embodiment two to ten two difference is: the carbon nanomaterial described in step 5 is a kind of or wherein several mixture in carbon nano-tube, Graphene, graphene oxide, intercalated graphite alkene, carbon nano-fiber and Nano carbon balls.Other are identical with embodiment two to ten two.

When carbon nanomaterial described in present embodiment is mixture, be mixed by any ratio between each component.

Embodiment 14: one of present embodiment and embodiment two to ten three difference is: the reaction initial soln described in step 6 is solvent or adopts solubility ammonium salt or ammoniacal liquor to add in solvent to be configured to NH ₄ ⁺concentration is the ammonia solution of 0.01mol/L ~ 2mol/L, and wherein said solvent is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, the methanol/ethanol aqueous solution, the methanol/acetone aqueous solution, the ethanol/acetone aqueous solution or methanol/ethanol/aqueous acetone solution; Wherein said solubility ammonium salt is a kind of or wherein several mixture in carbonic hydroammonium, ammonium carbonate, ammonium sulfate, ammonium hydrogen sulfate, ammonium chloride, ammonium phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate.Other are identical with embodiment two to ten three.

Embodiment 15: one of present embodiment and embodiment two to ten four difference is: the inert gas described in step 6 is argon gas, nitrogen or argon gas/nitrogen mixed gas.Other are identical with embodiment two to ten four.

Argon gas/nitrogen mixed gas described in present embodiment is mixed by arbitrary volume ratio by argon gas and nitrogen.

Embodiment 16: present embodiment is a kind of preparation method of presoma of doping carbon nano material, specifically completes according to the following steps: one, prepare raw material: according to chemical formula Mn _αco _βni _γm _ycO ₃by Mn element: Co element: Ni element: M element mol ratio is α: β: γ: y preparation soluble manganese salt, soluble cobalt, soluble nickel salt and soluble M salt; Two, prepare hybrid metal ion salt solution: soluble manganese salt step one prepared, soluble cobalt, soluble nickel salt and soluble M salt join in solvent and mixes, be configured to the hybrid metal ion salt solution that hybrid metal ion concentration is 0.01mol/L ~ 5mol/L; Three, precipitation reagent is prepared: added by soluble hydroxide in solvent, be configured to CO ₃ ^2-concentration is 0.1mol/L ~ 10mol/L precipitation reagent; Four, complexing agent is prepared: add in solvent by solubility ammonium salt or ammoniacal liquor, be configured to NH ₄ ⁺concentration is 0.1mol/L ~ 10mol/L complexing agent; Five, prepare carbon nanomaterial suspension: carbon nanomaterial is scattered in solvent, be configured to the carbon nanomaterial suspension that carbon nanomaterial concentration is 0.1mg/L ~ 50g/L; Six, coprecipitation reaction: the CO that hybrid metal ion concentration step 2 prepared is the hybrid metal ion salt solution of 0.01mol/L ~ 5mol/L, prepared by step 3 ₃ ^2-the NH that concentration is 0.1mol/L ~ 10mol/L precipitation reagent, prepared by step 4 ₄ ⁺the carbon nanomaterial suspension of concentration to be carbon nanomaterial concentration prepared by 0.1mol/L ~ 10mol/L complexing agent and step 5 be 0.1mg/L ~ 50g/L adds in the reactor that reaction initial soln is housed simultaneously, hybrid metal ion concentration prepared by step 2 is the speed that adds of the hybrid metal ion salt solution of 0.01mol/L ~ 5mol/L is 0.1mL/min ~ 1000mL/min, CO prepared by step 3 ₃ ^2-concentration is the speed that adds of 0.1mol/L ~ 10mol/L precipitation reagent is 0.1mL/min ~ 1000mL/min, NH prepared by step 4 ₄ ⁺concentration is the speed that adds of 0.1mol/L ~ 10mol/L complexing agent is 0.1mL/min ~ 1000mL/min, carbon nanomaterial concentration prepared by step 5 is the speed that adds of the carbon nanomaterial suspension of 0.1mg/L ~ 50g/L is 0.1mL/min ~ 500mL/min, and temperature be 20 DEG C ~ 90 DEG C, mixing speed to be 100rpm ~ 10000rpm, pH be 5 ~ 13 and inert gas shielding under react, namely obtain spherical precipitation thing; Seven, the dry process of washing: the spherical precipitation thing first adopting washed with de-ionized water step 6 to obtain, the pH cleaned to filtrate is neutrality, is then 20 DEG C ~ 150 DEG C in temperature and is dried to constant weight, namely obtain Uniform Doped carbon nanomaterial, molecular formula is Mn _αco _βni _γm _ycO ₃metal carbonate.

Described Mn described in present embodiment step one _αco _βni _γm _ycO ₃in 0 < α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ > 0, wherein said Mn _αco _βni _γm _ycO ₃middle M is the one or wherein several in Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and Sc.

Embodiment 17: the difference of present embodiment and embodiment 16 is: the soluble manganese salt described in step 2 is a kind of or wherein several mixture in manganese sulfate, manganese nitrate, manganese chloride, manganese sulfate hydrate, manganese nitrate hydrate and manganese chloride hydrate.Other are identical with embodiment 16.

Embodiment 18: one of present embodiment and embodiment 16 or 17 difference is: the soluble cobalt described in step 2 is a kind of or wherein several mixture in cobaltous sulfate, cobalt nitrate, cobalt chloride, cobaltous sulfate hydrate, cobalt nitrate hydrate and cobalt chloride hydrate.Other are identical with embodiment 16 or 17.

Embodiment 19: one of present embodiment and embodiment ten six to ten eight difference is: the soluble nickel salt described in step 2 is a kind of or wherein several mixture in nickelous sulfate, nickel nitrate, nickel chloride, nickel sulfate hydrate, nickel nitrate hydrate and nickel chloride hydrate.Other are identical with embodiment ten six to ten eight.

Embodiment 20: one of present embodiment and embodiment ten six to ten nine difference is: the soluble M salt described in step 2 is a kind of or wherein several mixture in sulfuric acid M, nitric acid M, chlorination M, sulfuric acid M hydrate, nitric acid M hydrate and chlorination M hydrate.Other are identical with embodiment ten six to ten nine.

Embodiment 21: one of present embodiment and embodiment ten six to two ten difference is: the solvent described in step 2 is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, the methanol/ethanol aqueous solution, the methanol/acetone aqueous solution, the ethanol/acetone aqueous solution or methanol/ethanol/aqueous acetone solution.Other are identical with embodiment ten six to two ten.

Embodiment 22: one of present embodiment and embodiment ten six to two 11 difference is: the solvent described in step 3 is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, the methanol/ethanol aqueous solution, the methanol/acetone aqueous solution, the ethanol/acetone aqueous solution or methanol/ethanol/aqueous acetone solution.Other are ten six to two ten one identical with embodiment.

Embodiment 23: one of present embodiment and embodiment ten six to two 12 difference is: the soluble carbonate salt described in step 3 is a kind of or wherein several mixture in sodium carbonate, sodium acid carbonate, potash, ammonium carbonate and carbonic hydroammonium.Other are ten six to two ten two identical with embodiment.

When soluble carbonate salt described in present embodiment is mixture, be mixed by any ratio between each component.

Embodiment 24: one of present embodiment and embodiment ten six to two 13 difference is: the solubility ammonium salt described in step 4 is a kind of or wherein several mixture in carbonic hydroammonium, ammonium carbonate, ammonium sulfate, ammonium hydrogen sulfate, ammonium chloride, ammonium phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate.Other are ten six to two ten three identical with embodiment.

Embodiment 25: one of present embodiment and embodiment ten six to two 14 difference is: the solvent described in step 4 is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, the methanol/ethanol aqueous solution, the methanol/acetone aqueous solution, the ethanol/acetone aqueous solution or methanol/ethanol/aqueous acetone solution.Other are ten six to two ten four identical with embodiment.

Embodiment 26: one of present embodiment and embodiment ten six to two 15 difference is: the solvent described in step 5 is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, the methanol/ethanol aqueous solution, the methanol/acetone aqueous solution, the ethanol/acetone aqueous solution or methanol/ethanol/aqueous acetone solution.Other are ten six to two ten five identical with embodiment.

Embodiment 27: one of present embodiment and embodiment ten six to two 16 difference is: the carbon nanomaterial described in step 5 is a kind of or wherein several mixture in carbon nano-tube, Graphene, graphene oxide, intercalated graphite alkene, carbon nano-fiber and Nano carbon balls.Other are ten six to two ten six identical with embodiment.

Embodiment 28: one of present embodiment and embodiment ten six to two 17 difference is: the reaction initial soln described in step 6 is solvent or adopts solubility ammonium salt or ammoniacal liquor to add in solvent to be configured to NH ₄ ⁺concentration is the ammonia solution of 0.01mol/L ~ 2mol/L, and wherein said solvent is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, the methanol/ethanol aqueous solution, the methanol/acetone aqueous solution, the ethanol/acetone aqueous solution or methanol/ethanol/aqueous acetone solution; Wherein said solubility ammonium salt is a kind of or wherein several mixture in carbonic hydroammonium, ammonium carbonate, ammonium sulfate, ammonium hydrogen sulfate, ammonium chloride, ammonium phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate.Other are ten six to two ten seven identical with embodiment.

Embodiment 29: one of present embodiment and embodiment ten six to two 18 difference is: the inert gas described in step 6 is argon gas, nitrogen or argon gas/nitrogen mixed gas.Other are ten six to two ten eight identical with embodiment.

Embodiment 30: present embodiment is a kind of spherical lithium metal oxide positive electrode, and spherical lithium metal oxide positive electrode is formed by the precursor power of the doping carbon nano material described in lithium-containing compound and embodiment one.

In the presoma of the doping carbon nano material described in present embodiment, the total amount of substance of metallic element is 1:(1 ~ 1.42 with the ratio of the amount of the Li elemental substance in the lithium-containing compound described in present embodiment)

The presoma of the doping carbon nano material described in present embodiment is Uniform Doped carbon nanomaterial, molecular formula is Mn _αco _βni _γm _y(OH) ₂metal hydroxides or Uniform Doped carbon nanomaterial, molecular formula be Mn _αco _βni _γm _ycO ₃metal carbonate; Wherein said Mn _αco _βni _γm _y(OH) ₂in 0 < α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ > 0, described Mn _αco _βni _γm _y(OH) ₂middle M is the one or wherein several in Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and Sc; Wherein said Mn _αco _βni _γm _ycO ₃in 0 < α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ > 0, described Mn _αco _βni _γm _ycO ₃middle M is the one or wherein several in Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and Sc.

Embodiment 31: the difference of embodiment and embodiment 30 is: described lithium-containing compound is a kind of or wherein several mixture in lithium hydroxide, lithium carbonate, lithium acetate, lithium oxalate, lithium nitrate and lithium citrate.Other are identical with embodiment 30.

When lithium-containing compound described in present embodiment is mixture, be mixed by any ratio between each component.

Embodiment 32: present embodiment is a kind of preparation method of spherical lithium metal oxide positive electrode, specifically complete according to the following steps: one, presoma preliminary treatment: by the presoma of the doping carbon nano material described in embodiment one at 200 DEG C ~ 800 DEG C pre-burning 1h ~ 12h, obtain presoma after preliminary treatment; Two, mixed lithium sintering: mixed with lithium-containing compound by presoma after preliminary treatment, is then 600 DEG C ~ 1200 DEG C roasting 3h ~ 36h in temperature, cools to room temperature with the furnace and namely obtain spherical lithium metal oxide positive electrode.

The presoma of the doping carbon nano material described in present embodiment step one is Uniform Doped carbon nanomaterial, molecular formula is Mn _αco _βni _γm _y(OH) ₂metal hydroxides or Uniform Doped carbon nanomaterial, molecular formula be Mn _αco _βni _γm _ycO ₃metal carbonate; Wherein said Mn _αco _βni _γm _y(OH) ₂in 0 < α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ > 0, described Mn _αco _βni _γm _y(OH) ₂middle M is the one or wherein several in Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and Sc; Wherein said Mn _αco _βni _γm _ycO ₃in 0 < α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ > 0, described Mn _αco _βni _γm _ycO ₃middle M is the one or wherein several in Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and Sc.

In the presoma of the doping carbon nano material described in present embodiment step one, the total amount of substance of metallic element is 1:(1 ~ 1.42 with the ratio of the amount of the Li elemental substance in the lithium-containing compound described in step 2).

The presoma preliminary treatment described in present embodiment can be ignored, the presoma of the doping carbon nano material described in direct employing embodiment one mixes with lithium-containing compound, then be 600 DEG C ~ 1200 DEG C roasting 3h ~ 36h in temperature, cool to room temperature with the furnace and namely obtain spherical lithium metal oxide positive electrode.When the presoma of the doping carbon nano material described in embodiment one is metal hydroxides, the presoma preliminary treatment directly mixed lithium sintering described in present embodiment generally can be ignored; When the presoma of the doping carbon nano material described in embodiment one is metal carbonate, need through the presoma preliminary treatment described in present embodiment, more mixed lithium sintering.

Embodiment 33: the difference of present embodiment and embodiment 32 is: a kind of or wherein several mixture in lithium-containing compound lithium hydroxide, lithium carbonate, lithium acetate, lithium oxalate, lithium nitrate and the lithium citrate described in step 2.Other are identical with embodiment 32.

Adopt following verification experimental verification effect of the present invention:

Test one: a kind of preparation method of presoma of doping carbon nano material, specifically completes according to the following steps: one, prepare raw material: according to chemical formula Mn _2/3co _1/6ni _1/6cO ₃by Mn element: Co element: Ni element: M element mol ratio is that 4:1:1 prepares manganese sulfate, cobaltous sulfate and nickelous sulfate; Two, prepare hybrid metal ion salt solution: manganese sulfate step one prepared, cobaltous sulfate and nickelous sulfate join in deionized water and mix, be configured to the hybrid metal ion salt solution that hybrid metal ion concentration is 1mol/L; Three, precipitation reagent is prepared: added by sodium carbonate in deionized water, be configured to CO ₃ ^2-concentration is 1mol/L precipitation reagent; Four, complexing agent is prepared: added by ammoniacal liquor in deionized water, be configured to NH ₄ ⁺concentration is 0.1mol/L complexing agent; Five, prepare carbon nanomaterial suspension: carbon nanomaterial is scattered in deionized water, be configured to the carbon nanomaterial suspension that carbon nanomaterial concentration is 1g/L; Six, coprecipitation reaction: the CO that hybrid metal ion concentration step 2 prepared is the hybrid metal ion salt solution of 1mol/L, prepared by step 3 ₃ ^2-the NH that concentration is 1mol/L precipitation reagent, prepared by step 4 ₄ ⁺the carbon nanomaterial suspension of concentration to be carbon nanomaterial concentration prepared by 0.1mol/L complexing agent and step 5 be 1g/L adds in the reactor that reaction initial soln is housed simultaneously, hybrid metal ion concentration prepared by step 2 is the speed that adds of the hybrid metal ion salt solution of 1mol/L is 500mL/min, CO prepared by step 3 ₃ ^2-concentration is the speed that adds of 1mol/L precipitation reagent is 500mL/min, NH prepared by step 4 ₄ ⁺concentration is the speed that adds of 0.1mol/L complexing agent is 500mL/min, carbon nanomaterial concentration prepared by step 5 is the speed that adds of the carbon nanomaterial suspension of 1g/L is 250mL/min, and temperature be 60 DEG C, mixing speed to be 1500rpm, pH be 7.5 and nitrogen protection under react, namely obtain spherical precipitation thing; Seven, the dry process of washing: the spherical precipitation thing first adopting washed with de-ionized water step 6 to obtain, the pH cleaned to filtrate is neutrality, is then 120 DEG C in temperature and is dried to constant weight, namely obtain Uniform Doped carbon nanomaterial, molecular formula is Mn _2/3co _1/6ni _1/6cO ₃metal carbonate.

Testing the reaction initial soln described in a step 6 is that ammoniacal liquor adds in deionized water and is configured to NH ₄ ⁺concentration is the ammonia solution of 0.05mol/L.

The volumetric ratio of the volume and reactor of testing the reaction initial soln described in a step 6 is 0.2:1.

Test a contrast test: one, prepare raw material: according to chemical formula Mn _2/3co _1/6ni _1/6cO ₃by Mn element: Co element: Ni element: M element mol ratio is that 4:1:1 prepares manganese sulfate, cobaltous sulfate and nickelous sulfate; Two, prepare hybrid metal ion salt solution: manganese sulfate step one prepared, cobaltous sulfate and nickelous sulfate join in deionized water and mix, be configured to the hybrid metal ion salt solution that hybrid metal ion concentration is 1mol/L; Three, precipitation reagent is prepared: added by sodium carbonate in deionized water, be configured to CO ₃ ^2-concentration is 1mol/L precipitation reagent; Four, complexing agent is prepared: added by ammoniacal liquor in deionized water, be configured to NH ₄ ⁺concentration is 0.1mol/L complexing agent; Five, coprecipitation reaction: the CO that hybrid metal ion concentration step 2 prepared is the hybrid metal ion salt solution of 1mol/L, prepared by step 3 ₃ ^2-concentration is NH prepared by 1mol/L precipitation reagent and step 4 ₄ ⁺concentration is that 0.1mol/L complexing agent adds in the reactor that reaction initial soln is housed simultaneously, and hybrid metal ion concentration prepared by step 2 is the speed that adds of the hybrid metal ion salt solution of 1mol/L is 500mL/min, CO prepared by step 3 ₃ ^2-concentration is the speed that adds of 1mol/L precipitation reagent is 500mL/min, NH prepared by step 4 ₄ ⁺concentration is the speed that adds of 0.1mol/L complexing agent is 500mL/min, and temperature be 60 DEG C, mixing speed to be 1500rpm, pH be 7.5 and nitrogen protection under react, namely obtain spherical precipitation thing; Six, the dry process of washing: the spherical precipitation thing first adopting washed with de-ionized water step 5 to obtain, the pH cleaned to filtrate is neutrality, be then 120 DEG C in temperature and be dried to constant weight, namely obtaining molecular formula is Mn _2/3co _1/6ni _1/6cO ₃metal carbonate.

The volumetric ratio of the volume and reactor of testing the reaction initial soln described in a contrast test step 5 is 0.2:1.

(Uniform Doped carbon nanomaterial, molecular formula are Mn to the presoma of the doping carbon nano material adopting X-ray diffractometer detection experiment one to prepare _2/3co _1/6ni _1/6cO ₃metal carbonate), testing result as shown in Figure 1, Fig. 1 be test one prepare spherical lithium metal oxide positive electrode XRD scheme, as seen in Figure 1 synthesized by material crystalline structure complete, without other impurity.

(Uniform Doped carbon nanomaterial, molecular formula are Mn to the presoma of the doping carbon nano material adopting scanning electron microscopy test one to prepare _2/3co _1/6ni _1/6cO ₃metal carbonate), as shown in Figure 2, Fig. 2 is the SEM figure that the presoma of doping carbon nano material prepared by test one amplifies 10000 times to testing result, and the precursor spherical degree can being observed doping carbon nano material prepared by test one by Fig. 2 is higher.

Test two: a kind of preparation method of spherical lithium metal oxide positive electrode, specifically complete according to the following steps: one, presoma preliminary treatment: the presoma of doping carbon nano material test one obtained, at 500 DEG C of pre-burning 12h, obtains presoma after preliminary treatment; Two, mixed lithium sintering: after preliminary treatment step one obtained, presoma mixes with lithium hydroxide, is then 900 DEG C of roasting 30h in temperature, cools to room temperature with the furnace and namely obtain spherical lithium metal oxide positive electrode.

Testing the total amount of substance of metallic element in the presoma testing the doping carbon nano material that obtains described in two steps one is 1:1.25 with the ratio of the amount of the Li elemental substance in the lithium hydroxide described in step 2.

Test two contrast tests: one, presoma preliminary treatment: be Mn by the molecular formula that test one contrast test obtains _2/3co _1/6ni _1/6cO ₃metal carbonate at 500 DEG C of pre-burning 12h, obtain presoma after preliminary treatment; Two, mixed lithium sintering: after preliminary treatment step one obtained, presoma mixes with lithium hydroxide, is then 900 DEG C of roasting 30h in temperature, cools to room temperature with the furnace and namely obtain spherical lithium metal oxide positive electrode.

Adopt spherical lithium metal oxide positive electrode prepared by X-ray diffractometer detection experiment two, testing result as shown in Figure 3, Fig. 3 is that spherical lithium metal oxide positive electrode XRD prepared by test two schemes, can find out that spherical lithium metal oxide positive electrode crystalline structure prepared by test two is complete by XRD data in Fig. 3, and 20 ~ 25 degree of range intervals can observe rich lithium material distinctive superlattice ordered structure fingerprint peaks significantly thus demonstrate adopt the method synthesized crystalline structure rich lithium material complete, free from foreign meter.

Adopt the spherical lithium metal oxide positive electrode of scanning electron microscopy test two preparation, testing result as shown in Figure 4, Fig. 4 is the SEM figure that the spherical lithium metal oxide positive electrode of test two preparation amplifies 5000 times, and the spherical lithium metal oxide anode material spherical degree can observed from Fig. 4 by testing two preparations is higher.

Spherical lithium metal oxide positive electrode prepared by the spherical lithium metal oxide positive electrode adopting new prestige high accuracy battery performance test system testing experiment two to prepare and test two contrast tests, model is used to be CR2025 button cell during test, employing metal lithium sheet is negative pole, the EC+DEC+DMC mixed system of electrolyte to be volume ratio containing 1mol/L-1LiPF6 be 1:1:1, uses microporous polypropylene membrane as barrier film.By the electrode plates for preparing, moisture and oxygen content are lower than in the glove box of 5ppm under an argon atmosphere, and be assembled into Li/ active material half-cell, battery carries out charge-discharge test with 0.1C multiplying power, and discharge and recharge interval is 2.0 ~ 4.6V.Testing result as shown in Figure 5, Fig. 5 is charging and discharging curve figure, in figure, A represents spherical lithium metal oxide positive electrode charge graph prepared by test two, in figure, B represents spherical lithium metal oxide anode material discharging curve chart prepared by test two, in figure, C represents spherical lithium metal oxide positive electrode charge graph prepared by test two contrast test, in figure, D represents spherical lithium metal oxide anode material discharging curve chart prepared by test two contrast test, can observe spherical lithium metal oxide positive electrode initial charge specific capacity prepared by test two contrast test by Fig. 5 is 324mAh/g, specific discharge capacity is 255mAh/g, coulombic efficiency is 78% first, the spherical lithium metal oxide positive electrode initial charge specific capacity of test two preparation is 335mAh/g, specific discharge capacity is 303mAh/g, coulombic efficiency is 90% first, and therefore compared with the spherical lithium metal oxide positive electrode prepared of the spherical lithium metal oxide positive electrode prepared of known test two and test two contrast test, coulombic efficiency has had lifting by a relatively large margin first.

Spherical lithium metal oxide positive electrode prepared by the spherical lithium metal oxide positive electrode adopting new prestige high accuracy battery performance test system testing experiment two to prepare and test two contrast tests, model is used to be CR2025 button cell during test, employing metal lithium sheet is negative pole, the EC+DEC+DMC mixed system of electrolyte to be volume ratio containing 1mol/L-1LiPF6 be 1:1:1, uses microporous polypropylene membrane as barrier film.By the electrode plates for preparing, moisture and oxygen content are lower than in the glove box of 5ppm under an argon atmosphere, and be assembled into Li/ active material half-cell, battery carries out charge-discharge test with 1C multiplying power, and discharge and recharge interval is 2.0 ~ 4.6V.Testing result as shown in Figure 6, Fig. 6 is high rate performance curve chart, in figure, A represents the high rate performance curve chart of spherical lithium metal oxide positive electrode prepared by test two, in figure, B represents the high rate performance curve chart of spherical lithium metal oxide positive electrode prepared by test two contrast test, and can observe spherical lithium metal oxide positive electrode 1C discharge capacity prepared by test two contrast test by Fig. 6 is 185mAh/g; Spherical lithium metal oxide positive electrode 1C discharge capacity prepared by test two is 218mAh/g, and compared with spherical lithium metal oxide positive electrode prepared by the spherical lithium metal oxide positive electrode of therefore known test two preparation and test two contrast test, high rate performance promotes 18%.

The new JZ-7 type tap density meter of essence is adopted to carry out spherical lithium metal oxide positive electrode, commercialization cobalt acid lithium and commercialization ternary material prepared by determination test two according to the requirement of GB GB/T5162-2006/ISO3953:1993 to the tap density of sample powder, testing result is as shown in table 1, known by the Data Comparison of table 1, the spherical lithium metal oxide positive electrode tap density testing two preparations is as can be seen from Table 1 better than commercialization ternary material, substantially reaches the tap density level of commercialization cobalt acid lithium.

Table 1

Sample	Tap density (g/cm ³)
		Commercialization cobalt acid lithium	2.3～2.6
Commercialization ternary material	2～2.2
		The spherical lithium metal oxide positive electrode of test two preparation	2.35

Test three: a kind of preparation method of presoma of doping carbon nano material, specifically completes according to the following steps: one, prepare raw material: according to chemical formula Mn _0.795co _0.1ni _0.1m _0.005(OH) ₂by Mn element: Co element: Ni element: M element mol ratio is that 7.95:1:1:0.05 prepares nickel nitrate, cobalt nitrate, manganese nitrate and aluminum nitrate; Two, prepare hybrid metal ion salt solution: nickel nitrate step one prepared, cobalt nitrate, manganese nitrate and aluminum nitrate join in deionized water and mix, be configured to the hybrid metal ion salt solution that hybrid metal ion concentration is 2mol/L; Three, precipitation reagent is prepared: added by NaOH in deionized water, be configured to OH ^-concentration is 2mol/L precipitation reagent; Four, complexing agent is prepared: add in deionized water by solubility ammonium salt or ammoniacal liquor, be configured to NH ₄ ⁺concentration is 0.15mol/L complexing agent; Five, prepare carbon nanomaterial suspension: carbon nanomaterial is scattered in deionized water, be configured to the carbon nanomaterial suspension that carbon nanomaterial concentration is 1.5g/L; Six, coprecipitation reaction: the OH that hybrid metal ion concentration step 2 prepared is the hybrid metal ion salt solution of 2mol/L, prepared by step 3 ^-the NH that concentration is 2mol/L precipitation reagent, prepared by step 4 ₄ ⁺the carbon nanomaterial suspension of concentration to be carbon nanomaterial concentration prepared by 0.15mol/L complexing agent and step 5 be 1.5g/L adds in the reactor that reaction initial soln is housed simultaneously, hybrid metal ion concentration prepared by step 2 is the speed that adds of the hybrid metal ion salt solution of 2mol/L is 500mL/min, OH prepared by step 3 ^-concentration is the speed that adds of 2mol/L precipitation reagent is 500mL/min, NH prepared by step 4 ₄ ⁺concentration is the speed that adds of 0.15mol/L complexing agent is 500mL/min, carbon nanomaterial concentration prepared by step 5 is the speed that adds of the carbon nanomaterial suspension of 1.5g/L is 250mL/min, and temperature be 60 DEG C, mixing speed to be 1200rpm, pH be 10.5 and inert gas shielding under react, namely obtain spherical precipitation thing; Seven, the dry process of washing: the spherical precipitation thing first adopting washed with de-ionized water step 6 to obtain, the pH cleaned to filtrate is neutrality, is then 120 DEG C in temperature and is dried to constant weight, namely obtain Uniform Doped carbon nanomaterial, molecular formula is Mn _0.795co _0.1ni _0.1m _0.005(OH) ₂metal hydroxides.

Testing the reaction initial soln described in three step 6 is that ammoniacal liquor adds in deionized water and is configured to NH ₄ ⁺concentration is the ammonia solution of 0.1mol/L.

The volumetric ratio of the volume and reactor of testing the reaction initial soln described in three step 6 is 0.75:1.

(Uniform Doped nano-carbon material, molecular formula are Mn to the presoma of the doping carbon nano material adopting scanning electron microscopy test three to prepare _0.795co _0.1ni _0.1m _0.005(OH) ₂metal hydroxides), testing result as shown in Figure 7, Fig. 7 be the presoma of doping carbon nano material amplify 10000 times SEM figure, can observe by testing three employing doped carbon nanometer pipe precursor sphericities higher by Fig. 7.

Test four: a kind of preparation method of spherical lithium metal oxide positive electrode, specifically complete according to the following steps: the presoma of doping carbon nano material test three obtained mixes with lithium hydroxide, then be 800 DEG C of roasting 30h in temperature, cool to room temperature with the furnace and namely obtain spherical lithium metal oxide positive electrode.

Testing the total amount of substance of metallic element in the presoma of the doping carbon nano material that three obtain described in this test procedure one is 1:1.05 with the ratio of the amount of the Li elemental substance in lithium hydroxide.

X-ray diffractometer is adopted to detect the spherical lithium metal oxide positive electrode of this test preparation, testing result as shown in Figure 8, Fig. 8 is that spherical lithium metal oxide positive electrode XRD prepared by test four schemes, can find out that synthesized material crystalline structure is complete, without other impurity by XRD data in Fig. 8.

Adopt the spherical lithium metal oxide positive electrode of scanning electron microscopy test four preparation, testing result as shown in Figure 9, Fig. 9 is the SEM figure that the spherical lithium metal oxide positive electrode of test four preparation amplifies 5000 times, and the spherical lithium metal oxide anode material spherical degree can observed from Fig. 9 by testing four preparations is higher.

The new JZ-7 type tap density meter of essence is adopted to carry out spherical lithium metal oxide positive electrode, commercialization cobalt acid lithium and commercialization ternary material prepared by determination test four according to the requirement of GB GB/T5162-2006/ISO3953:1993 to the tap density of sample powder, testing result is as shown in table 2, be better than commercialization ternary material by the known spherical lithium metal oxide positive electrode tap density testing four preparations as can be seen from Table 2 of the Data Comparison of table 2, substantially reach the tap density level of commercialization cobalt acid lithium.

Table 2

Sample	Tap density (g/cm ³)
		Commercialization cobalt acid lithium	2.3～2.6
Commercialization ternary material	2～2.2
		The spherical lithium metal oxide positive electrode of test four preparation	2.4

Test five: a kind of preparation method of presoma of doping carbon nano material, specifically completes according to the following steps: one, prepare raw material: according to chemical formula Mn _2/3co _1/6ni _1/6cO ₃by Mn element: Co element: Ni element: M element mol ratio is that 4:1:1 prepares manganese sulfate, cobaltous sulfate and nickelous sulfate; Two, prepare hybrid metal ion salt solution: manganese sulfate step one prepared, cobaltous sulfate and nickelous sulfate join in deionized water and mix, be configured to the hybrid metal ion salt solution that hybrid metal ion concentration is 1mol/L; Three, precipitation reagent is prepared: added by sodium carbonate in deionized water, be configured to CO ₃ ^2-concentration is 1mol/L precipitation reagent; Four, complexing agent is prepared: added by ammoniacal liquor in deionized water, be configured to NH ₄ ⁺concentration is 0.1mol/L complexing agent; Five, prepare carbon nanomaterial suspension: carbon nanomaterial is scattered in deionized water, be configured to the carbon nanomaterial suspension that carbon nanomaterial concentration is 1g/L; Six, coprecipitation reaction: the CO that hybrid metal ion concentration step 2 prepared is the hybrid metal ion salt solution of 1mol/L, prepared by step 3 ₃ ^2-the NH that concentration is 1mol/L precipitation reagent, prepared by step 4 ₄ ⁺the carbon nanomaterial suspension of concentration to be carbon nanomaterial concentration prepared by 0.1mol/L complexing agent and step 5 be 1g/L adds in the reactor that reaction initial soln is housed simultaneously, hybrid metal ion concentration prepared by step 2 is the speed that adds of the hybrid metal ion salt solution of 1mol/L is 500mL/min, CO prepared by step 3 ₃ ^2-concentration is the speed that adds of 1mol/L precipitation reagent is 500mL/min, NH prepared by step 4 ₄ ⁺concentration is the speed that adds of 0.1mol/L complexing agent is 500mL/min, carbon nanomaterial concentration prepared by step 5 is the speed that adds of the carbon nanomaterial suspension of 1g/L is 250mL/min, and temperature be 60 DEG C, mixing speed to be 1500rpm, pH be 7.5 and nitrogen protection under react, namely obtain spherical precipitation thing; Seven, the dry process of washing: the spherical precipitation thing first adopting washed with de-ionized water step 6 to obtain, the pH cleaned to filtrate is neutrality, is then 120 DEG C in temperature and is dried to constant weight, namely obtain Uniform Doped carbon nanomaterial, molecular formula is Mn _2/3co _1/6ni _1/6cO ₃metal carbonate.

Testing the reaction initial soln described in five step 6 is deionized water.

The volumetric ratio of the volume and reactor of testing the reaction initial soln described in five step 6 is 0.5:1.

Adopt the presoma of the doping carbon nano material of scanning electron microscopy test five preparation, testing result as shown in Figure 10, Figure 10 is the SEM figure that the presoma of doping carbon nano material prepared by test five amplifies 5000 times, as shown in Figure 10, although adopt aqueous solvent to be also the particle that sphericity is higher as precursor prepared by reaction initial soln, but it is more can not can be observed ball particle around spheric granules, be unfavorable for the raising of tap density.

The preparation method of test six, a kind of spherical lithium metal oxide positive electrode, specifically complete according to the following steps: one, presoma preliminary treatment: the presoma of doping carbon nano material test five obtained, at 500 DEG C of pre-burning 12h, obtains presoma after preliminary treatment; Two, mixed lithium sintering: after preliminary treatment step 2 obtained, presoma mixes with lithium hydroxide, is then 850 DEG C of roasting 30h in temperature, cools to room temperature with the furnace and namely obtain spherical lithium metal oxide positive electrode.

Testing the total amount of substance of metallic element in the presoma testing the doping carbon nano material that five obtain described in six steps one is 1:1.27 with the ratio of the amount of the Li elemental substance in the lithium hydroxide described in step 2.

The new JZ-7 type tap density meter of essence is adopted according to the requirement of GB GB/T5162-2006/ISO3953:1993, the tap density of sample powder to be carried out to the spherical lithium metal oxide positive electrode of determination test six preparation, commercialization cobalt acid lithium and commercialization ternary material, testing result is as shown in table 3, commercialization ternary material is better than by the spherical lithium metal oxide positive electrode tap density of the Data Comparison of table 3 known test six preparation, substantially the tap density level of commercialization cobalt acid lithium is reached, but owing to not becoming ball particle slightly many in material, the spherical lithium metal oxide positive electrode that its tap density is prepared a little less than test two.

Table 3

Sample	Tap density (g/cm ³)
		Commercialization cobalt acid lithium	2.3～2.6
Commercialization ternary material	2～2.2
		The spherical lithium metal oxide positive pole material of test six preparation	2.3

Test seven: a kind of preparation method of presoma of doping carbon nano material, specifically completes according to the following steps: one, prepare raw material: according to chemical formula Mn _1/3co _1/3ni _1/3cO ₃by Mn element: Co element: Ni element: M element mol ratio is that 1:1:1 prepares manganese sulfate, cobaltous sulfate and nickelous sulfate; Two, prepare hybrid metal ion salt solution: manganese sulfate step one prepared, cobaltous sulfate and nickelous sulfate join in deionized water and mix, be configured to the hybrid metal ion salt solution that hybrid metal ion concentration is 1mol/L; Three, precipitation reagent is prepared: added by sodium carbonate in deionized water, be configured to CO ₃ ^2-concentration is 1mol/L precipitation reagent; Four, complexing agent is prepared: added by ammoniacal liquor in deionized water, be configured to NH ₄ ⁺concentration is 0.1mol/L complexing agent; Five, prepare carbon nanomaterial suspension: carbon nanomaterial is scattered in deionized water, be configured to the carbon nanomaterial suspension that carbon nanomaterial concentration is 1g/L; Six, coprecipitation reaction: the CO that hybrid metal ion concentration step 2 prepared is the hybrid metal ion salt solution of 1mol/L, prepared by step 3 ₃ ^2-the NH that concentration is 1mol/L precipitation reagent, prepared by step 4 ₄ ⁺the carbon nanomaterial suspension of concentration to be carbon nanomaterial concentration prepared by 0.1mol/L complexing agent and step 5 be 1g/L adds in the reactor that reaction initial soln is housed simultaneously, hybrid metal ion concentration prepared by step 2 is the speed that adds of the hybrid metal ion salt solution of 1mol/L is 500mL/min, CO prepared by step 3 ₃ ^2-concentration is the speed that adds of 1mol/L precipitation reagent is 500mL/min, NH prepared by step 4 ₄ ⁺concentration is the speed that adds of 0.1mol/L complexing agent is 500mL/min, carbon nanomaterial concentration prepared by step 5 is the speed that adds of the carbon nanomaterial suspension of 1g/L is 250mL/min, and temperature be 60 DEG C, mixing speed to be 1500rpm, pH be 7.5 and nitrogen protection under react, namely obtain spherical precipitation thing; Seven, the dry process of washing: the spherical precipitation thing first adopting washed with de-ionized water step 6 to obtain, the pH cleaned to filtrate is neutrality, is then 120 DEG C in temperature and is dried to constant weight, namely obtain Uniform Doped carbon nanomaterial, molecular formula is Mn _1/3co _1/3ni _1/3cO ₃metal carbonate.

Testing the reaction initial soln described in seven step 6 is deionized water.

The volumetric ratio of the volume and reactor of testing the reaction initial soln described in seven step 6 is 0.02:1.

Test eight: a kind of preparation method of spherical lithium metal oxide positive electrode, specifically complete according to the following steps: one, presoma preliminary treatment: the presoma of doping carbon nano material test seven obtained, at 500 DEG C of pre-burning 12h, obtains presoma after preliminary treatment; Two, mixed lithium sintering: after preliminary treatment step 2 obtained, presoma mixes with lithium hydroxide, is then 800 DEG C of roasting 30h in temperature, cools to room temperature with the furnace and namely obtain spherical lithium metal oxide positive electrode.

Testing the total amount of substance of metallic element in the presoma testing the doping carbon nano material that seven obtain described in eight steps one is 1:1 with the ratio of the amount of the Li elemental substance in the lithium hydroxide described in step 2.

Claims

1. a presoma for doping carbon nano material, is characterized in that the presoma of doping carbon nano material is Uniform Doped carbon nanomaterial, molecular formula is Mn _αco _βni _γm _y(OH) ₂metal hydroxides or Uniform Doped carbon nanomaterial, molecular formula be Mn _αco _βni _γm _ycO ₃metal carbonate; Wherein said Mn _αco _βni _γm _y(OH) ₂in 0 < α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ > 0, described Mn _αco _βni _γm _y(OH) ₂middle M is the one or wherein several in Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and Sc; Wherein said Mn _αco _βni _γm _ycO ₃in 0 < α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ > 0, described Mn _αco _βni _γm _ycO ₃middle M is the one or wherein several in Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and Sc;

The presoma of described doping carbon nano material is for the preparation of spherical lithium metal oxide positive electrode, the described concrete preparation process of spherical lithium metal oxide positive electrode is as follows: one, presoma preliminary treatment: by the presoma of doping carbon nano material at 200 DEG C ~ 800 DEG C pre-burning 1h ~ 12h, obtain pretreated presoma; Two, mixed lithium sintering: mixed with lithium-containing compound by pretreated presoma, is then 600 DEG C ~ 1200 DEG C roasting 3h ~ 36h in temperature, cools to room temperature with the furnace and namely obtain spherical lithium metal oxide positive electrode; In the presoma of the doping carbon nano material described in step one, the total amount of substance of metallic element is 1:(1 ~ 1.42 with the ratio of the amount of the Li elemental substance in the lithium-containing compound described in step 2).

2. the preparation method of the presoma of a kind of doping carbon nano material as claimed in claim 1, is characterized in that the preparation method of the presoma of doping carbon nano material completes according to the following steps: one, prepare raw material: according to chemical formula Mn _αco _βni _γm _y(OH) ₂by Mn element: Co element: Ni element: M element mol ratio is α: β: γ: y preparation soluble manganese salt, soluble cobalt, soluble nickel salt and soluble M salt; Two, prepare hybrid metal ion salt solution: soluble manganese salt step one prepared, soluble cobalt, soluble nickel salt and soluble M salt join in solvent and mixes, be configured to the hybrid metal ion salt solution that hybrid metal ion concentration is 0.01mol/L ~ 5mol/L; Three, prepare precipitation reagent: added by soluble hydroxide in solvent, being configured to OH-concentration is 0.1mol/L ~ 10mol/L precipitation reagent; Four, complexing agent is prepared: add in solvent by solubility ammonium salt or ammoniacal liquor, be configured to NH ₄ ⁺concentration is 0.1mol/L ~ 10mol/L complexing agent; Five, prepare carbon nanomaterial suspension: carbon nanomaterial is scattered in solvent, be configured to the carbon nanomaterial suspension that carbon nanomaterial concentration is 0.1mg/L ~ 50g/L; Six, coprecipitation reaction: the OH that hybrid metal ion concentration step 2 prepared is the hybrid metal ion salt solution of 0.01mol/L ~ 5mol/L, prepared by step 3 ^-the NH that concentration is 0.1mol/L ~ 10mol/L precipitation reagent, prepared by step 4 ₄ ⁺the carbon nanomaterial suspension of concentration to be carbon nanomaterial concentration prepared by 0.1mol/L ~ 10mol/L complexing agent and step 5 be 0.1mg/L ~ 50g/L adds in the reactor that reaction initial soln is housed simultaneously, hybrid metal ion concentration prepared by step 2 is the speed that adds of the hybrid metal ion salt solution of 0.01mol/L ~ 5mol/L is 0.1mL/min ~ 1000mL/min, OH prepared by step 3 ^-concentration is the speed that adds of 0.1mol/L ~ 10mol/L precipitation reagent is 0.1mL/min ~ 1000mL/min, NH prepared by step 4 ₄ ⁺concentration is the speed that adds of 0.1mol/L ~ 10mol/L complexing agent is 0.1mL/min ~ 1000mL/min, carbon nanomaterial concentration prepared by step 5 is the speed that adds of the carbon nanomaterial suspension of 0.1mg/L ~ 50g/L is 0.1mL/min ~ 500mL/min, and temperature be 20 DEG C ~ 90 DEG C, mixing speed to be 100rpm ~ 10000rpm, pH be 5 ~ 13 and inert gas shielding under react, namely obtain spherical precipitation thing; Seven, the dry process of washing: the spherical precipitation thing first adopting washed with de-ionized water step 6 to obtain, the pH cleaned to filtrate is neutrality, is then 20 DEG C ~ 150 DEG C in temperature and is dried to constant weight, namely obtain Uniform Doped carbon nanomaterial, molecular formula is Mn _αco _βni _γm _y(OH) ₂metal hydroxides; Described Mn described in step one _αco _βni _γm _y(OH) ₂in 0 < α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ > 0, wherein said Mn _αco _βni _γm _y(OH) ₂middle M is the one or wherein several in Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and Sc; The volume of the reaction initial soln described in step 6 and the volumetric ratio of reactor are (0.001 ~ 0.8): 1.

3. the preparation method of the presoma of a kind of doping carbon nano material according to claim 2, is characterized in that the soluble manganese salt described in step 2 is a kind of or wherein several mixture in manganese sulfate, manganese nitrate, manganese chloride, manganese sulfate hydrate, manganese nitrate hydrate and manganese chloride hydrate; Soluble cobalt described in step 2 is a kind of or wherein several mixture in cobaltous sulfate, cobalt nitrate, cobalt chloride, cobaltous sulfate hydrate, cobalt nitrate hydrate and cobalt chloride hydrate; Soluble nickel salt described in step 2 is a kind of or wherein several mixture in nickelous sulfate, nickel nitrate, nickel chloride, nickel sulfate hydrate, nickel nitrate hydrate and nickel chloride hydrate; Soluble M salt described in step 2 is a kind of or wherein several mixture in sulfuric acid M, nitric acid M, chlorination M, sulfuric acid M hydrate, nitric acid M hydrate and chlorination M hydrate; Solvent described in step 2 is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, methanol/ethanol mixed aqueous solution, methanol acetone mixed aqueous solution, ethanol acetone mixed aqueous solution or methanol/ethanol acetone mixed aqueous solution; Solvent described in step 3 is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, methanol/ethanol mixed aqueous solution, methanol acetone mixed aqueous solution, ethanol acetone mixed aqueous solution or methanol/ethanol acetone mixed aqueous solution; Soluble hydroxide described in step 3 is a kind of or wherein several mixture in NaOH, potassium hydroxide, lithium hydroxide and barium hydroxide; Solubility ammonium salt described in step 4 is a kind of or wherein several mixture in carbonic hydroammonium, ammonium carbonate, ammonium sulfate, ammonium hydrogen sulfate, ammonium chloride, ammonium phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate; Solvent described in step 4 is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, methanol/ethanol mixed aqueous solution, methanol acetone mixed aqueous solution, ethanol acetone mixed aqueous solution or methanol/ethanol acetone mixed aqueous solution; Solvent described in step 5 is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, methanol/ethanol mixed aqueous solution, methanol acetone mixed aqueous solution, ethanol acetone mixed aqueous solution or methanol/ethanol acetone mixed aqueous solution; Carbon nanomaterial described in step 5 is a kind of or wherein several mixture in carbon nano-tube, Graphene, graphene oxide, intercalated graphite alkene, carbon nano-fiber and Nano carbon balls; Reaction initial soln described in step 6 is solvent or adopts solubility ammonium salt or ammoniacal liquor to add in solvent to be configured to NH ₄ ⁺concentration is the ammonia solution of 0.01mol/L ~ 2mol/L, wherein said solvent is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, methanol/ethanol mixed aqueous solution, methanol acetone mixed aqueous solution, ethanol acetone mixed aqueous solution or methanol/ethanol acetone mixed aqueous solution, and wherein said solubility ammonium salt is a kind of or wherein several mixture in carbonic hydroammonium, ammonium carbonate, ammonium sulfate, ammonium hydrogen sulfate, ammonium chloride, ammonium phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate; Inert gas described in step 6 is argon gas, nitrogen or argon gas/nitrogen mixed gas.

4. the preparation method of the presoma of a kind of doping carbon nano material as claimed in claim 1, is characterized in that the preparation method of the presoma of doping carbon nano material completes according to the following steps: one, prepare raw material: according to chemical formula Mn _αco _βni _γm _ycO ₃by Mn element: Co element: Ni element: M element mol ratio is α: β: γ: y preparation soluble manganese salt, soluble cobalt, soluble nickel salt and soluble M salt; Two, prepare hybrid metal ion salt solution: soluble manganese salt step one prepared, soluble cobalt, soluble nickel salt and soluble M salt join in solvent and mixes, be configured to the hybrid metal ion salt solution that hybrid metal ion concentration is 0.01mol/L ~ 5mol/L; Three, precipitation reagent is prepared: added by soluble carbonate salt in solvent, be configured to CO ₃ ^2-concentration is 0.1mol/L ~ 10mol/L precipitation reagent; Four, complexing agent is prepared: add in solvent by solubility ammonium salt or ammoniacal liquor, be configured to NH ₄ ⁺concentration is 0.1mol/L ~ 10mol/L complexing agent; Five, prepare carbon nanomaterial suspension: carbon nanomaterial is scattered in solvent, be configured to the carbon nanomaterial suspension that carbon nanomaterial concentration is 0.1mg/L ~ 50g/L; Six, coprecipitation reaction: the CO that hybrid metal ion concentration step 2 prepared is the hybrid metal ion salt solution of 0.01mol/L ~ 5mol/L, prepared by step 3 ₃ ^2-the NH that concentration is 0.1mol/L ~ 10mol/L precipitation reagent, prepared by step 4 ₄ ⁺the carbon nanomaterial suspension of concentration to be carbon nanomaterial concentration prepared by 0.1mol/L ~ 10mol/L complexing agent and step 5 be 0.1mg/L ~ 50g/L adds in the reactor that reaction initial soln is housed simultaneously, hybrid metal ion concentration prepared by step 2 is the speed that adds of the hybrid metal ion salt solution of 0.01mol/L ~ 5mol/L is 0.1mL/min ~ 1000mL/min, CO prepared by step 3 ₃ ^2-concentration is the speed that adds of 0.1mol/L ~ 10mol/L precipitation reagent is 0.1mL/min ~ 1000mL/min, NH prepared by step 4 ₄ ⁺concentration is the speed that adds of 0.1mol/L ~ 10mol/L complexing agent is 0.1mL/min ~ 1000mL/min, carbon nanomaterial concentration prepared by step 5 is the speed that adds of the carbon nanomaterial suspension of 0.1mg/L ~ 50g/L is 0.1mL/min ~ 500mL/min, and temperature be 20 DEG C ~ 90 DEG C, mixing speed to be 100rpm ~ 10000rpm, pH be 5 ~ 13 and inert gas shielding under react, namely obtain spherical precipitation thing; Seven, the dry process of washing: the spherical precipitation thing first adopting washed with de-ionized water step 6 to obtain, the pH cleaned to filtrate is neutrality, is then 20 DEG C ~ 150 DEG C in temperature and is dried to constant weight, namely obtain Uniform Doped carbon nanomaterial, molecular formula is Mn _αco _βni _γm _ycO ₃metal carbonate; Described Mn described in step one _αco _βni _γm _ycO ₃in 0 < α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ > 0, wherein said Mn _αco _βni _γm _ycO ₃middle M is the one or wherein several in Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and Sc; The volume of the reaction initial soln described in step 6 and the volumetric ratio of reactor are (0.001 ~ 0.8): 1.

5. the preparation method of the presoma of a kind of doping carbon nano material according to claim 4, is characterized in that the soluble manganese salt described in step 2 is a kind of or wherein several mixture in manganese sulfate, manganese nitrate, manganese chloride, manganese sulfate hydrate, manganese nitrate hydrate and manganese chloride hydrate; Soluble cobalt described in step 2 is a kind of or wherein several mixture in cobaltous sulfate, cobalt nitrate, cobalt chloride, cobaltous sulfate hydrate, cobalt nitrate hydrate and cobalt chloride hydrate; Soluble nickel salt described in step 2 is a kind of or wherein several mixture in nickelous sulfate, nickel nitrate, nickel chloride, nickel sulfate hydrate, nickel nitrate hydrate and nickel chloride hydrate; Soluble M salt described in step 2 is a kind of or wherein several mixture in sulfuric acid M, nitric acid M, chlorination M, sulfuric acid M hydrate, nitric acid M hydrate and chlorination M hydrate; Solvent described in step 2 is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, methanol/ethanol mixed aqueous solution, methanol acetone mixed aqueous solution, ethanol acetone mixed aqueous solution or methanol/ethanol acetone mixed aqueous solution; Solvent described in step 3 is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, methanol/ethanol mixed aqueous solution, methanol acetone mixed aqueous solution, ethanol acetone mixed aqueous solution or methanol/ethanol acetone mixed aqueous solution; Soluble carbonate salt described in step 3 is a kind of or wherein several mixture in sodium carbonate, sodium acid carbonate, potash, ammonium carbonate and carbonic hydroammonium; Solubility ammonium salt described in step 4 is a kind of or wherein several mixture in carbonic hydroammonium, ammonium carbonate, ammonium sulfate, ammonium hydrogen sulfate, ammonium chloride, ammonium phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate; Solvent described in step 4 is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, methanol/ethanol mixed aqueous solution, methanol acetone mixed aqueous solution, ethanol acetone mixed aqueous solution or methanol/ethanol acetone mixed aqueous solution; Solvent described in step 5 is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, methanol/ethanol mixed aqueous solution, methanol acetone mixed aqueous solution, ethanol acetone mixed aqueous solution or methanol/ethanol acetone mixed aqueous solution; Carbon nanomaterial described in step 5 is a kind of or wherein several mixture in carbon nano-tube, Graphene, graphene oxide, intercalated graphite alkene, carbon nano-fiber and Nano carbon balls; Reaction initial soln described in step 6 is solvent or adopts solubility ammonium salt or ammoniacal liquor to add in solvent to be configured to NH ₄ ⁺concentration is the ammonia solution of 0.01mol/L ~ 2mol/L, wherein said solvent is deionized water, methanol aqueous solution, ethanol water, aqueous acetone solution, methanol/ethanol mixed aqueous solution, methanol acetone mixed aqueous solution, ethanol acetone mixed aqueous solution or methanol/ethanol acetone mixed aqueous solution, and wherein said solubility ammonium salt is a kind of or wherein several mixture in carbonic hydroammonium, ammonium carbonate, ammonium sulfate, ammonium hydrogen sulfate, ammonium chloride, ammonium phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate; Inert gas described in step 6 is argon gas, nitrogen or argon gas/nitrogen mixed gas.

6. a spherical lithium metal oxide positive electrode, is characterized in that spherical lithium metal oxide positive electrode is formed by the precursor power of lithium-containing compound and doping carbon nano material according to claim 1; In the presoma of described doping carbon nano material, the total amount of substance of metallic element is 1:(1 ~ 1.42 with the ratio of the amount of the Li elemental substance in described lithium-containing compound); The presoma of described doping carbon nano material is Uniform Doped carbon nanomaterial, molecular formula is Mn _αco _βni _γm _y(OH) ₂metal hydroxides or Uniform Doped carbon nanomaterial, molecular formula be Mn _αco _βni _γm _ycO ₃metal carbonate; Wherein said Mn _αco _βni _γm _y(OH) ₂in 0 < α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ > 0, described Mn _αco _βni _γm _y(OH) ₂middle M is the one or wherein several in Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and Sc; Wherein said Mn _αco _βni _γm _ycO ₃in 0 < α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ > 0, described Mn _αco _βni _γm _ycO ₃middle M is the one or wherein several in Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and Sc;

Described spherical lithium metal oxide positive electrode is prepared according to the following steps: one, presoma preliminary treatment: by the presoma of doping carbon nano material according to claim 1 at 200 DEG C ~ 800 DEG C pre-burning 1h ~ 12h, obtain pretreated presoma; Two, mixed lithium sintering: mixed with lithium-containing compound by pretreated presoma, is then 600 DEG C ~ 1200 DEG C roasting 3h ~ 36h in temperature, cools to room temperature with the furnace and namely obtain spherical lithium metal oxide positive electrode.

7. the spherical lithium metal oxide positive electrode of one according to claim 6, is characterized in that described lithium-containing compound is a kind of or wherein several mixture in lithium hydroxide, lithium carbonate, lithium acetate, lithium oxalate, lithium nitrate and lithium citrate.

8. the preparation method of a kind of spherical lithium metal oxide positive electrode as claimed in claim 6, it is characterized in that the preparation method of spherical lithium metal oxide positive electrode completes according to the following steps: one, presoma preliminary treatment: by the presoma of doping carbon nano material according to claim 1 at 200 DEG C ~ 800 DEG C pre-burning 1h ~ 12h, obtain pretreated presoma; Two, mixed lithium sintering: mixed with lithium-containing compound by pretreated presoma, is then 600 DEG C ~ 1200 DEG C roasting 3h ~ 36h in temperature, cools to room temperature with the furnace and namely obtain spherical lithium metal oxide positive electrode; The presoma of the doping carbon nano material described in step one is Uniform Doped carbon nanomaterial, molecular formula is Mn _αco _βni _γm _y(OH) ₂metal hydroxides or Uniform Doped carbon nanomaterial, molecular formula be Mn _αco _βni _γm _ycO ₃metal carbonate; Wherein said Mn _αco _βni _γm _y(OH) ₂in 0 < α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ > 0, described Mn _αco _βni _γm _y(OH) ₂middle M is the one or wherein several in Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and Sc; Wherein said Mn _αco _βni _γm _ycO ₃in 0 < α≤1,0≤β≤1,0≤γ≤1,0≤y≤0.5, and alpha+beta+γ+y=1, β+γ > 0, described Mn _αco _βni _γm _ycO ₃middle M is the one or wherein several in Cr, Al, Fe, Mg, Ag, Ti, Cu, V, Y, La, Tm, Gd, Ho, Ce, Lu, Yb and Sc; In the presoma of the doping carbon nano material described in step one, the total amount of substance of metallic element is 1:(1 ~ 1.42 with the ratio of the amount of the Li elemental substance in the lithium-containing compound described in step 2).

9. the preparation method of a kind of spherical lithium metal oxide positive electrode according to claim 8, is characterized in that a kind of or wherein several mixture in lithium-containing compound lithium hydroxide, lithium carbonate, lithium acetate, lithium oxalate, lithium nitrate and the lithium citrate described in step 2.