A single-phase, gassing-inhibited manganese-based positive electrode lithium supplement material and its preparation method and application

Abstract

The present invention belongs to the technical field of lithium-ion battery materials, and relates to a single-phase, gassing-inhibited manganese-based positive electrode lithium supplement material, a preparation method and an application thereof. The chemical formula of the manganese-based positive electrode lithium supplement material is Li x (Mn y M1 a M2 b )O4, wherein M1 is selected from at least one of K, Ca, Mg, Sn, Ti, Ni, V, Cr, Co and Cu; M2 is selected from at least one of Zr, Al, Nb, Mo, Fe, B, Si and Zn; during preparation, firstly, lithium source, manganese source and other metal / non-metal source are weighed and ball-milled according to the molar ratio of each element in the chemical formula to obtain a precursor powder; then, the precursor powder of step S1 is calcined and cooled to obtain a single-phase, gas evolution suppressed manganese-based positive electrode lithium replenishing material; when used in a lithium ion battery, the first cycle charge specific capacity is ≥550mAh / g, and the discharge specific capacity is ≤30mAh / g. The product of the present invention has a high effective lithium replenishing capacity; the preparation method is simple; and when used, it can significantly improve the first cycle coulomb efficiency and cycle performance of the lithium ion battery.

Description

Technical Field

[0001] The present invention belongs to the technical field of lithium-ion battery materials and relates to a single-phase, gassing-inhibited manganese-based positive electrode lithium supplement material and a preparation method and application thereof. Background Art

[0002] Lithium-ion batteries have been widely used in consumer electronics, electric transportation, large-scale energy storage and other fields. In response to the increasing demand for applications, lithium-ion batteries need to have a longer service life and higher energy density. The reduction in cycle life and loss of energy density of lithium-ion batteries is partly due to the formation of a solid electrolyte interface phase (SEI) on the negative electrode side during the first cycle formation process. SEI is mainly composed of organic / inorganic compounds containing lithium, and the lithium required for film formation mainly comes from the active lithium in the positive electrode material. In order to compensate for the loss of active lithium in the positive electrode material to improve the cycle life and energy density of lithium batteries, lithium replenishment of the electrode is an effective means. Positive electrode lithium replenishment is mainly achieved by adding a small amount of positive electrode lithium replenisher to the slurry during the homogenization process. This method is not only simple to operate, but also can achieve precise lithium replenishment by regulating the amount of lithium replenisher added. It is a lithium replenishment method with great application prospects.

[0003] Positive electrode lithium supplements are typically compounds with a high lithium content. These substances typically release a large amount of lithium ions only during the first charge cycle, while only a small amount of lithium ions can be reversibly reinserted during the first discharge cycle and do not participate in subsequent electrochemical reactions. Therefore, lithium supplements are generally required to have a high first-cycle charge (de-lithiation) specific capacity and a low first-cycle coulombic efficiency to achieve better lithium supplementation. However, most current lithium supplements suffer from low first-cycle de-lithiation specific capacity, high cost, and easy gassing.

[0004] In response to the development needs of high-energy-density lithium-ion batteries, manganese-based lithium supplement materials have attracted attention due to their low cost and high theoretical capacity advantages, but their inherent defects have seriously restricted their industrial applications. Manganese-based lithium supplements represented by anti-fluorite Li6MnO4 face two key technical bottlenecks in practical applications: First, the synthesis conditions of single-phase Li6MnO4 are harsh, and it is easy to decompose and generate MnO and Li2O impurities during the high-temperature preparation process. These inactive impurities will reduce the effective lithium supplement capacity. The second is the serious gas production problem caused by the irreversible release of lattice oxygen. The delithiation process of Li6MnO4 involves Mn 2+ Oxidation and lattice oxygen (O 2- ) charge compensation, in which O²⁻ will form O2 n-Intermediate states such as (0 < n < 4) finally escape in the form of oxygen molecules. Oxygen release has double destructiveness: on the one hand, O2 directly participates in the oxidation and decomposition of the electrolyte, triggering the ring-opening reaction of carbonate solvents, generating a large amount of gases such as CO2 and CO; on the other hand, free oxygen atoms will penetrate to the negative electrode to exacerbate the reconstruction of the SEI film, forming a porous and loose interfacial layer, resulting in continuous consumption of active lithium. There are no relevant patents and literature reports on the synthesis of single-phase Li6MnO4.

[0005] For example, in Literature 1 (Chem. Commun., 2017, 53, 8324–8327.), the highest specific charge capacity in the first charge can reach 1154.2 mAh / g, but the charge cut-off voltage is relatively high, at 4.6 V, and there is still much room for improvement.

[0006] In Literature 2 (J. Power Sources, 2018, 400, 549–555.), the Li5FeO4 lithium supplement material can reach a specific charge capacity of 665 mAh / g at a charge cut-off voltage of 4.5 V. However, adding 10 wt% of the material can only compensate for 9.2% of the lithium loss.

[0007] Literature 3 (J. Electrochem. Soc., 2012, 159, A1329.) shows that the de-lithiation capacity of the lithium supplement agent is relatively low, only 326 mAh / g, and there is still much room for improvement.

[0008] In Literature 4 (ACS Sustain. Chem. Eng., 2023, 11, 1044.), at a charge cut-off voltage of 4.4 V, the charge capacity is 465 mAh / g. However, it has a relatively high reversible capacity of 149.6 mAh / g. Therefore, the actual lithium capacity used for compensation is relatively low, only 215.4 mAh / g.

[0009] The following table shows the data of Literature 1 to Literature 4:

[0010] Table 1

[0011] Lithium supplement materials First cycle charging capacity [mAh / g] First cycle discharge capacity [mAh / g] First-cycle coulombic efficiency of lithium-replenishing materials [%] Lithium supplement material content [wt%] First cycle coulombic efficiency of full battery before pre-lithiation [%] First cycle coulombic efficiency of full battery after pre-lithiation [%] literature <![CDATA[Li2O2]]> 1154.2 / / 2.0 67.50% 80.00% 1 <![CDATA[L i5 FeO4]]> 665 / / 10.0 67.80% 87.0% 2 <![CDATA[Li6CoO4]]> 326 13 3.9 15.0 66.50% 85% 3 <![CDATA[Li2Cu 0.1 Ni0 .9 O2]]> 465 149.6 30.0 13.0 92% 96.60% 4

[0012] Patent CN202411758424.4 discloses a lithium supplement material, its preparation method, a cathode material and a secondary battery, which solves the problems of residual alkali on the surface of the secondary battery and high gas production. However, the total gas production during high-temperature aging of this patent is at least 61 mL / g at the lowest, and there is still room for optimization.

[0013] Patent CN202410879412.0 discloses a lithium-supplementing material, its preparation method, positive electrode material and secondary battery, which solve the problem of high decomposition voltage of lithium-supplementing materials. The decomposition voltage of this patent is 4.0V~4.3V, but the first-cycle charging capacity is low, only 400~450mAh / g, and there is still much room for improvement.

[0014] Therefore, it is of great significance to study a single-phase, gassing-inhibited manganese-based positive electrode lithium supplement material and its preparation method and application to solve the problems existing in the prior art. Summary of the Invention

[0015] The present invention aims to address the challenges of the prior art by providing a single-phase, gassing-suppressed manganese-based cathode lithium-replenishing material, its preparation method, and its application. This invention overcomes the mutually exclusive challenges of high decomposition voltage and lattice oxygen loss in Li6MnO4 lithium-replenishing materials through a multi-element synergistic doping strategy. Its core design involves the precise control of two types of functional elements: a structural stabilizer (at least one of K, Ca, Mg, Sn, Ti, Ni, V, Cr, Co, and Cu) induces three-dimensional lattice distortion through large-radius ions, lowering the sintering temperature and suppressing impurity formation; and a lattice oxygen stabilizer (at least one of Zr, Al, Nb, Mo, Fe, B, Si, and Zn) enhances the metal-oxygen bond through strong covalent bonds (e.g., Zr-O bond energy of 77 kJ / mol) and multiple metal coordination, stabilizing the lattice oxygen structure and effectively suppressing lattice oxygen release. Ultimately, the material has a higher first-cycle lithium removal capacity with no obvious oxygen release. Adding 2~10wt% can compensate for the 10~40% lithium loss of the silicon-based negative electrode, breaking through the technical bottleneck of traditional manganese-based materials that "high capacity must have high oxygen evolution."

[0016] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0017] A single-phase, gassing-inhibited manganese-based cathode lithium supplement material with the general chemical formula Li x (Mn y M1 a M2 b )O4, wherein 2≤x≤6, 0.05≤y≤1, 0.01≤a≤0.94, 0.01≤b≤0.94, M1 is selected from at least one of K, Ca, Mg, Sn, Ti, Ni, V, Cr, Co and Cu, and as a structural stabilizer, its ionic radius is the same as that of Mn 2⁺The difference is obvious. The sintering temperature is reduced and the formation of Li2O / MnO impurities is suppressed through three-dimensional lattice distortion. M2 is selected from at least one of Zr, Al, Nb, Mo, Fe, B, Si and Zn. As a lattice oxygen stabilizer, it strengthens the metal-oxygen bonding force through strong covalent bonds and multiple metal coordination, reducing lattice oxygen precipitation. The total doping amount (a+b) of M1 and M2 is controlled to 0.02≤a+b≤0.95, and the manganese content y and the total content of M1 and M2 satisfy the relationship: y+a+b≤1.

[0018] The materials are added according to the chemical structure ratio, with a relative excess of 1~10 mol% of lithium source to compensate for the intrinsic defects of high-temperature lithium source volatilization; but when there is too much lithium source, there will be too much residual alkali on the surface of the lithium-supplementing material, causing the slurry to gel and unable to be coated.

[0019] The present invention also provides a method for preparing the above-mentioned single-phase, gassing-inhibited manganese-based positive electrode lithium supplement material, comprising the following steps:

[0020] Step S1: weighing a lithium source, a manganese source, and other metal / non-metal sources according to the molar ratio of each element in the chemical formula, and ball-milling and mixing them to obtain a precursor powder;

[0021] Step S2: evenly spread the precursor powder of step S1 in an alumina crucible, place it in a tube furnace for calcination, and obtain a single-phase, gas evolution-inhibited manganese-based positive electrode lithium supplement material after cooling.

[0022] As described above, in the method for preparing a single-phase, gassing-inhibited manganese-based positive electrode lithium supplement material, in step S1, the lithium source is one or more of lithium peroxide (Li2O2), lithium oxalate (Li2C2O4), lithium oxide (Li2O), lithium hydroxide (LiOH), lithium sulfate (Li2SO4), lithium nitrate (LiNO3), lithium carbonate (Li2CO3) and lithium acetate (CH3COOLi), and the manganese source is one or more of manganese oxide (MnO, Mn2O3, Mn3O4) and manganese hydroxide (Mn(OH)2).

[0023] As the preferred technical solution:

[0024] In the above-mentioned method for preparing a single-phase, gas evolution suppressed manganese-based positive lithium supplement material, in step S1, the other metal / non-metal sources include: a potassium source is one or more of potassium oxide (K2O), potassium superoxide (KO2) and potassium hydroxide (KOH); a calcium source is one or more of calcium oxide (CaO), calcium peroxide (CaO2) and calcium hydroxide (Ca(OH)2); a magnesium source is one or more of magnesium oxide (MgO), magnesium peroxide (MgO2) and magnesium hydroxide (Mg(OH)2); a tin source is tin dioxide (SnO2), stannous oxide (SnO) and tin hydroxide (Sn(OH)4); the titanium source is one or more of titanium dioxide (TiO2) and titanium hydroxide (Ti(OH)4); the vanadium source is one or more of vanadium pentoxide (V2O5) and vanadium hydroxide (V(OH)3 / V(OH)4); the cobalt source is one or more of cobalt oxide (CoO), cobalt hydroxide (Co(OH)2) and cobalt trioxide (Co2O3); the chromium source is one or more of chromium trioxide (Cr2O3) and chromium hydroxide (Cr(OH)3); the nickel source is nickel oxide The copper source is one or more of copper oxide (CuO), copper hydroxide (Cu(OH)2) and basic copper carbonate (Cu2(OH)2CO3); the zirconium source is one or more of zirconium dioxide (ZrO2) and zirconium hydroxide (Zr(OH)4); the aluminum source is one or more of aluminum oxide (Al2O3), aluminum hydroxide (Al(OH)3) and aluminum oxyhydroxide (AlO(OH)); the niobium source is niobium pentoxide (Nb2O5) and niobium hydroxide (Nb(OH)5) The molybdenum source is one or more of molybdenum trioxide (MoO3) and molybdenum hydroxide (MoO(OH)3); the iron source is one or more of iron oxide (Fe2O3) and iron hydroxide (Fe(OH)2); the boron source is one or more of boron trioxide (B2O3) and boron hydroxide (B(OH)3); the silicon source is one or more of silicon dioxide (SiO2) and silicon hydroxide (Si(OH)4); the zinc source is one or more of zinc oxide (ZnO), zinc nitrate (Zn(NO3)2) and zinc hydroxide (Zn(OH)2).

[0025] In the method for preparing a single-phase, gassing-inhibited manganese-based positive lithium supplement material as described above, in step S1, the ball milling mixing speed is 200-1000 rpm, the time is 1-20 hours, the ball milling beads are zirconium beads, and the ball-to-material ratio is 10-25:1.

[0026] When the ball mill speed is lower than 200rpm, the energy provided by the ball mill is insufficient to fully crush the lithium source, manganese source and dopant source; when the ball mill speed is higher than 1000rpm (i.e. the critical speed of the ball mill), the grinding beads will adhere to the inner wall of the ball mill and rotate, and lose the effect of crushing, resulting in no obvious change in the particle size of the lithium source, manganese source and dopant source raw materials, further affecting the size of the manganese-based positive electrode lithium supplement material.

[0027] If the ball milling time is less than 1 hour, the raw materials of lithium source, manganese source and dopant source will not be sufficiently crushed (generally speaking, the larger the particle size of the raw materials, the larger the particles of the prepared lithium supplement material); if the ball milling time is higher than 20 hours, the particle size of lithium source, manganese source and dopant source will no longer change, and too long ball milling time may introduce zirconium source contamination products into the ball milling beads.

[0028] When the ball-to-material ratio is lower than 10, the increase in material has a stronger cushioning effect on the impact of the ball milling beads. At the same time, the number of ball milling beads decreases, and the number of collisions and frictions between the ball milling beads decreases accordingly, which will also make the crushing effect of the lithium source, manganese source and dopant source raw materials unsatisfactory, resulting in larger particle size; when the ball-to-material ratio is higher than 25, the useless work of friction and collision between the ball milling beads and the ball milling beads and the inner wall of the ball milling jar increases, reducing the crushing efficiency of the lithium source, manganese source and dopant source raw materials, while increasing energy consumption and wear of the ball milling balls and the ball milling barrel.

[0029] In the method for preparing a single-phase, gas evolution-inhibited manganese-based positive electrode lithium supplement material as described above, in step S2, the calcination conditions are: calcination temperature of 500-1000°C, heating rate of 1-10°C / min, calcination time of 10-24h, calcination atmosphere of nitrogen or argon, and cooling after calcination.

[0030] A heating rate lower than 1°C / min helps reduce thermal stress and improve the uniformity of the sintered product. However, a slower heating rate increases preparation time and reduces production efficiency. A heating rate higher than 10°C / min leads to unevenness during sintering and increased thermal stress.

[0031] If the sintering time is less than 10 hours, the reactants fail to fully react and sinter, resulting in the presence of unreacted raw materials in the product, reducing the purity of the product; if the sintering time is more than 24 hours, the lithium element in the lithium source material will volatilize or decompose, producing lithium-deficient products, and long-term high-temperature treatment may cause the raw material particles to agglomerate and the grains to grow, thereby increasing the grain size of the final product, resulting in a larger particle size of the synthesized manganese-based positive electrode lithium supplement material.

[0032] In the method for preparing a single-phase, gassing-inhibited manganese-based positive lithium supplement material as described above, the cooling conditions in step S2 are: slowly cooling to 30°C at a cooling rate of 1-5°C / min under a nitrogen or argon atmosphere, and maintaining it for 2-10 hours.

[0033] The present invention also provides a use of the above-mentioned single-phase, gassing-inhibited manganese-based positive electrode lithium replenishing material in a lithium-ion battery. The single-phase, gassing-inhibited manganese-based positive electrode lithium replenishing material has a first-cycle charge specific capacity ≥550mAh / g, a discharge specific capacity ≤30mAh / g, and a coulombic efficiency (ICE) of 0.7~8.5%. The lower the ICE value, the higher the irreversible capacity and the better the lithium replenishing effect. The oxygen release amount is ≤1.2mL / g at a charge cut-off voltage of 4.3V. An addition amount of 2~10wt% can compensate for 10~40% of the lithium loss of the silicon-based negative electrode.

[0034] Principle of the invention:

[0035] The present invention discloses a high-capacity, low-gassing single-phase manganese-based positive lithium supplement material, the general chemical formula of which is Li x (Mn y M1 a M2 b )O4 (2≤x≤6, 0.05≤y≤1, 0.01≤a≤0.94, 0.01≤b≤0.94), through a synergistic design of structural stability and oxygen locking, overcomes the technical bottleneck of traditional lithium-ion supplement materials in balancing high capacity and safety. The innovative nature of this material lies in the doping of a structural stabilizer element (M1) (at least one of K, Ca, Mg, Sn, Ti, Ni, V, Cr, Co, and Cu) into the bulk phase of the manganese-based cathode lithium supplement material. This ion size difference induces three-dimensional lattice distortion, inhibiting the formation of impurities during synthesis and buffering volume deformation during charge and discharge, preventing particle cracking and the resulting decrease in lithium release efficiency. Simultaneously, a lattice oxygen stabilizer element (M2) (M2 selected from at least one of Zr, Al, Nb, Mo, Fe, B, Si, and Zn) is doped onto the surface of the manganese-based cathode lithium supplement material. This strong chemical bond creates an oxygen anchoring network, enhancing the metal-oxygen bond energy and fundamentally suppressing oxygen evolution under high voltage. Furthermore, the M1 / M2 electron orbital interaction further strengthens the localized nature of lattice oxygen (M1-O-M2), further addressing the oxygen escape problem. This structural design successfully produced a lithium-supplementing material with an irreversible capacity ≥550mAh / g and an oxygen release rate ≤1.2mL / g at a charge cutoff voltage of 4.3V. This overcomes the key scientific challenge of the mutual constraints between high capacity and lattice oxygen stability in traditional lithium-rich oxide lithium-supplementing materials. When used as a lithium-supplementing agent, this material can significantly improve the first-cycle coulombic efficiency and cycling performance of lithium-ion batteries.

[0036] In the present invention, the structural stabilizer M1 element and the lattice oxygen stabilizer M2 element are introduced into the lithium supplement material by using the partitioned doping method. The principle of partitioned doping is to optimize the element spatial distribution of the single-phase material in a staged temperature field by utilizing the difference in element migration energy barriers.

[0037] This method precisely exploits the difference in migration energy barriers between the M1 and M2 elements to preferentially achieve uniform bulk doping of the M1 element at low temperatures (500-700°C), constructing a rigid [MO6] framework to widen lithium-ion channels and mitigate volume deformation. Subsequently, at high temperatures (800-1000°C), the steric hindrance effect induced by M1 doping forces the high-barrier M2 element to kinetically concentrate on the material surface, forming an oxygen anchoring layer. This strategy, through staged thermodynamic-kinetic coupled control, overcomes the limitations of conventional co-doping processes, such as disordered element distribution and low bonding strength, achieving the fabrication of a single-phase manganese-based cathode lithium-supplementing material and integrating the functionalities of interfacial oxygen fixation.

[0038] Beneficial effects:

[0039] (1) The present invention provides a method for preparing a single-phase, gassing-inhibited manganese-based positive electrode lithium replenishing material. Through a multi-metal synergistic doping strategy, the synergistic optimization of crystal structure stability and electrochemical performance is achieved in an inverse fluorite-type manganese-based positive electrode lithium replenishing material. The large-radius ion-induced three-dimensional lattice distortion reduces the sintering temperature and inhibits the formation of impurity phases, thereby improving the delithiation capacity. More importantly, through the electronic regulation of strongly electronegative elements and the stable MO covalent bond network, the stability of lattice oxygen is greatly improved, the oxygen loss phenomenon at high potential is effectively suppressed, and the anion redox process remains highly reversible.

[0040] (2) The present invention provides a method for preparing a single-phase, gassing-inhibited manganese-based positive electrode lithium replenishing material. The preparation method is simple, and the prepared manganese-based lithium replenishing agent is expected to be used in lithium-ion battery positive electrode materials and lithium-ion batteries.

[0041] (3) The single-phase, gas evolution-inhibited manganese-based positive electrode lithium supplement material of the present invention can effectively compensate for the loss of active lithium in the positive electrode material during the first cycle of charge and discharge of the lithium battery, which is beneficial to improving the energy density and long cycle life of the lithium battery.

[0042] (4) The application of a single-phase, gassing-inhibited manganese-based positive electrode lithium replenishment material of the present invention has a better lithium replenishment efficiency. Only 2wt% of the material needs to be added to compensate for 10% of the lithium loss, showing a better material utilization efficiency. This synergistic optimization of high specific capacity and controllable ICE characteristics provides an innovative solution for accurately compensating for the 10~40% lithium loss of silicon-based negative electrodes. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 is the X-ray diffraction (XRD) curve of the manganese-based positive electrode lithium supplement material, where Figure 1 (a) and (b) correspond to Comparative Example 1 and Example 1, respectively;

[0044] Figure 2 This is a scanning electron microscope (SEM) image of the manganese-based positive electrode lithium replenishing material of Example 2;

[0045] Figure 3 This is the SEM image of the manganese-based positive electrode lithium supplement material, Figure 3 (a) and (b) correspond to Comparative Example 1 and Example 3, respectively;

[0046] Figure 4 Li5(Mn 0.6 Ni 0.2 Zr 0.2 ) Transmission scanning electron microscopy (TEM) image of O4 and element distribution map of three elements: Zr, Mn and Ni;

[0047] Figure 5 The first cycle charge and discharge curves of the manganese-based positive electrode lithium supplement material of Comparative Example 2 and Example 14 of the present invention;

[0048] Figure 6 This is the in-situ differential electrochemical mass spectrometry (DEMS) corresponding to the first cycle charging curve of the manganese-based positive electrode lithium replenishing material in Example 6. DETAILED DESCRIPTION

[0049] Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiments are only used to illustrate the present invention and are not used in limiting the scope of the present invention.In addition, should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall equally within the scope limited by the appended claims of the application.

[0050] The detection methods of the relevant properties in the embodiments and comparative examples of the present invention are as follows:

[0051] The charge and discharge specific capacity of manganese-based positive electrode lithium replenishing material: The electrode sheet of the manganese-based positive electrode lithium replenishing material and the lithium sheet are assembled into a half-cell, and then placed on a shelf in a constant temperature chamber at 25°C for 6 hours, and then charged to 4.3V at a constant current of 0.03C (1C=550mAh / g), and then discharged to 3V at 0.05C, and then tested using the Wuhan Blue Electric CT2001A system; the measured charge and discharge specific capacity of the half-cell is the charge and discharge specific capacity of the manganese-based positive electrode lithium replenishing material.

[0052] The capacity retention rate of a lithium-ion full battery after 300 cycles is tested as follows: the assembled full battery is placed on a shelf in a constant temperature chamber at 25°C for 6 hours, and then charged to 4.2V at a constant current of 0.05C (1C = 200mAh / g) and discharged to 3V at 0.05C for the first cycle. The battery is then charged to 4.2V at a constant current of 0.5C (1C = 200mAh / g) and discharged to 3V at 0.5C. The charge and discharge specific capacity of the full battery is tested using a Wuhan Blue Electric CT2001A.

[0053] The gas generation detection method for single-phase, gassing-suppressed manganese-based cathode materials involves assembling a DEMS-specific cell in an argon glove box with the prepared manganese-based cathode material. The cell is then connected to a mass spectrometer (such as the Cirrus3-XD, Wuhan Planck) to ensure airtightness. The cell is first left at 25°C for 6 hours to record a baseline. The cell is then charged to 4.3V at a constant current of 0.03C (1C = 550mAh / g) while simultaneously monitoring the oxygen gas signal.

[0054] The equipment used for high-speed ball milling in the examples is a QM-0.4L ball mill from Henan Flier Instrument Equipment Co., Ltd.

[0055] The sources of some of the substances of the present invention are as follows:

[0056] Conductive additive: Shenzhen Kejing Zhida Technology Co., Ltd., model: Super P Li, battery grade.

[0057] Polyvinylidene fluoride binder: SOLVAY, PVDF 5130.

[0058] N-Methylpyrrolidone: NMP, J&K Scientific, AR.

[0059] Cathode material: LiNi 0.83 Co 0.12 Mn 0.05 O2, Rongbai Technology Co., Ltd., S85E.

[0060] Binder: Guangdong Candlelight New Energy Technology Co., Ltd., dedicated to high nickel products.

[0061] Anode material: BYD, BSO-2.

[0062] Lithium polyacrylate binder: LiPAA, Sichuan Yindile Technology Co., Ltd., LA136D.

[0063] Example 1

[0064] A single-phase, gassing-inhibited manganese-based cathode lithium supplement material Li6(Mn 0.8 Ca 0.1 Al 0.1 )O4 preparation method, comprising the following steps:

[0065] (1) Li2O, MnO, CaO, and Al2O3 were weighed and mixed according to the molar ratio of the chemical formula to obtain a precursor powder with a particle size of 300-500 nm;

[0066] The excess amount of Li2O was 6 mol%, the ball milling speed was 650 rpm, the time was 5 h, the ball milling beads were zirconium beads, and the ball-to-material ratio was 25:1;

[0067] (2) Under a nitrogen atmosphere, the precursor powder of step (1) is evenly spread in an alumina crucible and placed in a tube furnace for calcination;

[0068] The calcination conditions are as follows: calcination temperature is 900°C, heating rate is 3°C / min, and calcination time is 15h;

[0069] (3) The product of step (2) was slowly cooled to 30°C at a cooling rate of 1°C / min under a nitrogen atmosphere and maintained for 5 hours. After cooling, a single-phase, gas evolution-inhibited manganese-based positive lithium supplement material with a particle size of 1-4 μm was obtained, namely Li6(Mn 0.8 Ca 0.1 Al 0.1 )O4.

[0070] Comparative Example 1

[0071] A method for preparing a manganese-based positive electrode lithium supplement material Li6MnO4 is basically the same as that in Example 1, except that the raw materials in step (1) do not contain CaO and Al2O3.

[0072] Example 2

[0073] A single-phase, gassing-suppressed manganese-based cathode lithium supplement material Li 5.2 (Mn 0.7 Ti 0.1 Nb 0.2 )O4 preparation method, comprising the following steps:

[0074] (1) Li2C2O4, Mn(OH)2, TiO2, and Nb2O5 were weighed and mixed by ball milling according to the molar ratio of the chemical formula to obtain a precursor powder with a particle size of 100-200 nm;

[0075] The lithium source was in excess of 1 mol%, the ball milling speed was 200 rpm, the time was 20 h, the ball milling beads were zirconium beads, and the ball-to-material ratio was 20:1;

[0076] (2) Under an argon atmosphere, the precursor powder of step (1) is evenly spread in an alumina crucible and placed in a tube furnace for calcination;

[0077] The calcination conditions are as follows: calcination temperature is 500°C, heating rate is 1°C / min, and calcination time is 12h;

[0078] (3) The product of step (2) was slowly cooled to 30°C at a cooling rate of 5°C / min under an argon atmosphere and maintained at that temperature for 3 hours. After cooling, the product was obtained as shown in FIG. Figure 2 The single-phase, gas evolution suppressed manganese-based positive electrode lithium supplement material with a particle size of 2~5μm, namely Li 5.2(Mn 0.7 Ti 0.1 Nb 0.2 )O4.

[0079] Example 3

[0080] A single-phase, gassing-inhibited manganese-based cathode lithium supplement material Li5(Mn 0.6 Ni 0.2 Zr 0.2 )O4 preparation method, comprising the following steps:

[0081] (1) Li2CO3, MnO, NiO and Zr(OH)4 were weighed and mixed by ball milling according to the molar ratio of the chemical formula to obtain a precursor powder with a particle size of 200-300 nm;

[0082] The lithium source was in excess of 2 mol%, the ball milling speed was 300 rpm, the time was 12 h, the ball milling beads were zirconium beads, and the ball-to-material ratio was 15:1;

[0083] (2) Under a nitrogen atmosphere, the precursor powder of step (1) is evenly spread in an alumina crucible and placed in a tube furnace for calcination;

[0084] The calcination conditions are as follows: calcination temperature is 600°C, heating rate is 5°C / min, and calcination time is 18h;

[0085] (3) The product of step (2) was slowly cooled to 30°C at a cooling rate of 5°C / min under a nitrogen atmosphere and maintained at that temperature for 6 hours. After cooling, a single-phase, gas evolution inhibited manganese-based positive electrode lithium supplement material with a particle size of 1-3 μm was obtained, namely Li5(Mn 0.6 Ni 0.2 Zr 0.2 )O4.

[0086] like Figure 4 As shown, transmission scanning electron microscopy observation confirmed that nickel (Ni) was successfully doped into the bulk phase of the manganese-based positive electrode lithium supplement material as a structural stabilizer, while zirconium (Zr) was uniformly distributed on the surface of the material as a lattice oxygen stabilizer.

[0087] Example 4

[0088] A single-phase, gassing-inhibited manganese-based cathode lithium supplement material Li3(Mn 0.9 Sn 0.05 Si 0.05 )O4 preparation method, comprising the following steps:

[0089] (1) Li2O, MnO, SnO2 and Si(OH)4 were weighed and mixed according to the molar ratio of the chemical formula to obtain a precursor powder with a particle size of 50-100 nm;

[0090] The lithium source was in excess of 4 mol%, the ball milling speed was 500 rpm, the time was 8 h, the ball milling beads were zirconium beads, and the ball-to-material ratio was 10:1;

[0091] (2) Under an argon atmosphere, the precursor powder of step (1) is evenly spread in an alumina crucible and placed in a tube furnace for calcination;

[0092] The calcination conditions are as follows: calcination temperature is 700°C, heating rate is 6°C / min, and calcination time is 20h;

[0093] (3) The product of step (2) was slowly cooled to 30°C at a cooling rate of 2°C / min under an argon atmosphere and maintained for 8 hours. After cooling, a single-phase, gas evolution-inhibited manganese-based positive electrode lithium supplement material with a particle size of 3-6 μm was obtained, namely Li3(Mn 0.9 Sn 0.05 Si 0.05 )O4.

[0094] Example 5

[0095] A single-phase, gassing-inhibited manganese-based cathode lithium supplement material Li2(Mn 0.5 Co 0.3 Fe 0.2 )O4 preparation method, comprising the following steps:

[0096] (1) Li2C2O4, Mn3O4, Co(OH)2 and Fe(OH)2 were weighed and mixed by ball milling according to the molar ratio of the chemical formula to obtain a precursor powder with a particle size of 400~600nm;

[0097] The lithium source was in excess of 5 mol%, the ball milling speed was 800 rpm, the time was 3 h, the ball milling beads were zirconium beads, and the ball-to-material ratio was 18:1;

[0098] (2) Under a nitrogen atmosphere, the precursor powder of step (1) is evenly spread in an alumina crucible and placed in a tube furnace for calcination;

[0099] The calcination conditions are as follows: calcination temperature is 800°C, heating rate is 8°C / min, and calcination time is 24h;

[0100] (3) The product of step (2) was slowly cooled to 30°C at a cooling rate of 3°C / min under a nitrogen atmosphere and maintained for 2 hours. After cooling, a single-phase, gas evolution-inhibited manganese-based positive electrode lithium supplement material with a particle size of 4-8 μm was obtained, namely Li2(Mn 0.5 Co 0.3 Fe 0.2 )O4.

[0101] Example 6

[0102] A single-phase, gassing-inhibited manganese-based cathode lithium supplement material Li6(Mn 0.05 K 0.45 B 0.5 )O4 preparation method, comprising the following steps:

[0103] (1) Li2O2, MnO, K2O, and B2O3 were weighed and mixed by ball milling according to the molar ratio of the chemical formula to obtain a precursor powder with a particle size of 800-1000 nm;

[0104] The lithium source was in excess of 10 mol%, the ball milling speed was 1000 rpm, the time was 1 h, the ball milling beads were zirconium beads, and the ball-to-material ratio was 22:1;

[0105] (2) Under an argon atmosphere, the precursor powder of step (1) is evenly spread in an alumina crucible and placed in a tube furnace for calcination;

[0106] The calcination conditions are as follows: calcination temperature is 1000°C, heating rate is 10°C / min, and calcination time is 10h;

[0107] (3) The product of step (2) was slowly cooled to 30°C at a cooling rate of 2°C / min under an argon atmosphere and maintained for 10 hours. After cooling, a single-phase, gas evolution-inhibited manganese-based positive lithium supplement material with a particle size of 0.5-2 μm was obtained, namely Li6(Mn 0.05 K 0.45 B 0.5 )O4.

[0108] like Figure 6 As shown in Figure 5, almost no oxygen generation was observed during the DEMS test, and the oxygen evolution reaction activity of the material was confirmed to be significantly inhibited.

[0109] Example 7

[0110] A single-phase, gassing-suppressed manganese-based cathode lithium supplement material Li 3.5 (Mn 0.75 Mg 0.15 Si 0.1 )O4 preparation method, comprising the following steps:

[0111] (1) LiOH, MnO, Mg(OH)2, and SiO2 were weighed and mixed according to the molar ratio of the chemical formula, and ball milled to obtain a precursor powder with a particle size of 150-250 nm;

[0112] The ball milling speed was 400 rpm, the time was 10 h, and the ball-to-material ratio was 12:1.

[0113] (2) Under an argon atmosphere, the precursor powder of step (1) is evenly spread in an alumina crucible and placed in a tube furnace for calcination;

[0114] The calcination conditions are as follows: calcination temperature is 550°C, heating rate is 4°C / min, and calcination time is 22 hours;

[0115] (3) The product of step (2) was slowly cooled to 30°C at a cooling rate of 1.5°C / min under an argon atmosphere and maintained for 10 hours. After cooling, a single-phase, gas evolution-inhibited manganese-based positive electrode lithium supplement material with a particle size of 2.5-5 μm was obtained, namely Li 3.5 (Mn 0.75 Mg 0.15 Si 0.1 )O4.

[0116] Example 8

[0117] A single-phase, gassing-suppressed manganese-based cathode lithium supplement material Li 4.8 (Mn 0.65 V 0.2 B 0.15 )O4 preparation method, comprising the following steps:

[0118] (1) LiNO3, MnO, V2O5, and B2O3 were weighed and mixed according to the molar ratio of the chemical formula to obtain a precursor powder with a particle size of 350-450 nm;

[0119] The ball milling speed was 700 rpm, the time was 6 hours, and the ball-to-material ratio was 18:1;

[0120] (2) Under a nitrogen atmosphere, the precursor powder of step (1) is evenly spread in an alumina crucible and placed in a tube furnace for calcination;

[0121] The calcination conditions are as follows: calcination temperature is 750°C, heating rate is 7°C / min, and calcination time is 14 hours;

[0122] (3) The product of step (2) was slowly cooled to 30°C at a cooling rate of 4°C / min under a nitrogen atmosphere and maintained for 4 hours. After cooling, a single-phase, gas evolution inhibited manganese-based positive electrode lithium supplement material with a particle size of 1.5-4 μm was obtained, namely Li 4.8 (Mn 0.65 V 0.2 B 0.15 )O4.

[0123] Example 9

[0124] A single-phase, gassing-suppressed manganese-based cathode lithium supplement material Li 2.8 (Mn 0.55 Cu0.3 Zn 0.15 )O4 preparation method, comprising the following steps:

[0125] (1) Li2SO4, MnO, CuO, and ZnO were weighed and mixed according to the molar ratio of the chemical formula to obtain a precursor powder with a particle size of 600-800 nm;

[0126] The ball milling speed was 900 rpm, the time was 2.5 hours, and the ball-to-material ratio was 14:1;

[0127] (2) Under an argon atmosphere, the precursor powder of step (1) is evenly spread in an alumina crucible and placed in a tube furnace for calcination;

[0128] The calcination conditions are as follows: calcination temperature is 850°C, heating rate is 9°C / min, and calcination time is 16 hours;

[0129] (3) The product of step (2) was slowly cooled to 30°C at a cooling rate of 3.5°C / min under an argon atmosphere and maintained for 3.5 hours. After cooling, a single-phase, gas evolution inhibited manganese-based positive electrode lithium supplement material with a particle size of 3-7 μm was obtained, namely Li 2.8 (Mn 0.55 Cu 0.3 Zn 0.15 )O4.

[0130] Example 10

[0131] A single-phase, gassing-suppressed manganese-based cathode lithium supplement material Li 5.2 (Mn 0.5 Cr 0.25 Si 0.25 )O4 preparation method, comprising the following steps:

[0132] (1) Li2O, MnO, Cr2O3 and SiO2 were weighed and mixed according to the molar ratio of the chemical formula to obtain a precursor powder with a particle size of 100-150 nm;

[0133] The ball milling speed was 250 rpm, the time was 15 h, and the ball-to-material ratio was 22:1.

[0134] (2) Under a nitrogen atmosphere, the precursor powder of step (1) is evenly spread in an alumina crucible and placed in a tube furnace for calcination;

[0135] The calcination conditions are as follows: first calcination at 500°C for 10 hours, then calcination at 800°C for 14 hours; the heating rate is 2°C / min;

[0136] (3) The product of step (2) was slowly cooled to 30°C at a cooling rate of 1°C / min under a nitrogen atmosphere and maintained for 10 hours. After cooling, a single-phase, gas evolution inhibited manganese-based positive electrode lithium supplement material with a particle size of 0.8-2 μm was obtained, namely Li 5.2 (Mn 0.5 Cr 0.25 Si 0.25 )O4.

[0137] Example 11

[0138] A single-phase, gassing-inhibited manganese-based cathode lithium supplement material Li6(Mn 0.1 K 0.45 B 0.45 )O4 preparation method, comprising the following steps:

[0139] (1) CH3COOLi, Mn2O3, KOH, and B2O3 were weighed and mixed by ball milling according to the molar ratio of the chemical formula to obtain a precursor powder with a particle size of 900-1000 nm;

[0140] The ball milling speed was 1000 rpm, the time was 1.5 hours, and the ball-to-material ratio was 24:1;

[0141] (2) Under an argon atmosphere, the precursor powder of step (1) is evenly spread in an alumina crucible and placed in a tube furnace for calcination;

[0142] The calcination conditions are as follows: calcination temperature is 1000°C, heating rate is 10°C / min, and calcination time is 11 hours;

[0143] (3) The product of step (2) was slowly cooled to 30°C at a cooling rate of 5°C / min under an argon atmosphere and maintained at this temperature for 2.8 hours. After cooling, a single-phase, gas evolution-inhibited manganese-based positive electrode lithium supplement material with a particle size of 0.5-1.5 μm was obtained, namely Li6(Mn 0.1 K 0.45 B 0.45 )O4.

[0144] Example 12

[0145] The application of a single-phase, gassing-inhibited manganese-based cathode lithium supplement material in a lithium-ion battery comprises the following specific steps:

[0146] (1) Preparation of manganese-based positive electrode lithium supplement material pole piece: The manganese-based positive electrode lithium supplement material Li6 (Mn 0.8 Ca 0.1 Al 0.1)O4, conductive additives and polyvinylidene fluoride binder are uniformly dispersed in solvent N-methylpyrrolidone to form a slurry, and the slurry is coated on aluminum foil and dried to obtain a pole piece of manganese-based positive electrode lithium supplement material.

[0147] (2) Test of the charge and discharge specific capacity of manganese-based positive electrode lithium replenishing materials: The electrode and lithium sheet of the manganese-based positive electrode lithium replenishing material are assembled into a half-cell, and then placed on a shelf in a constant temperature chamber at 25°C for 6 hours, and then charged to 4.3V at a constant current of 0.03C (1C=550mAh / g), and then discharged to 3V at 0.05C, and then tested using the Wuhan Blue Electric CT2001A system; the measured charge and discharge specific capacity of the half-cell is the charge and discharge specific capacity of the manganese-based positive electrode lithium replenishing material.

[0148] (3) Preparation of positive electrode manganese-based lithium-supplementing material composite electrode: the positive electrode material (LiNi 0.83 Co 0.12 Mn 0.05 O2), the manganese-based positive electrode lithium replenishing material of Example 1, the conductive additive and the binder are placed in an NMP solvent in a mass ratio of 86:4:5:5 and mixed, wherein the mass fraction of NMP is 50wt%, to form a uniformly dispersed slurry; then, the slurry is coated on an aluminum foil, and after drying, a positive electrode manganese-based lithium replenishing material composite electrode sheet is obtained.

[0149] (4) Preparation of negative electrode sheets: The negative electrode material, conductive additive, and lithium polyacrylate binder were mixed in deionized water at a mass ratio of 90:5:5, where the mass fraction of deionized water was 50 wt%, to form a uniform slurry; then, the slurry was coated on the surface of copper foil and dried to obtain the negative electrode sheet.

[0150] (5) Assembly of the full battery: The positive electrode manganese-based lithium supplement material composite electrode is used as the positive electrode, the negative electrode is used as the negative electrode, the positive and negative electrode capacity ratio is 1:1.2, Celgard2050 is selected as the separator, the electrolyte model selected is LB-008 from Duoduo Reagent Company, the electrolyte addition amount is 40µl, and the full battery is assembled.

[0151] The single-phase, gas evolution-inhibited manganese-based positive electrode lithium supplement material has a first-cycle charge capacity of 720mAh / g, a discharge capacity of 20mAh / g, a coulombic efficiency of 2.7%, and an oxygen release of 0.6mL / g at a charge cut-off voltage of 4.3V. An addition of 4wt% can compensate for the 17.4% lithium loss of the silicon-based negative electrode; the capacity retention rate of the lithium-ion full battery after 300 cycles is 95%.

[0152] Comparative Example 2

[0153] The application of a manganese-based positive electrode lithium supplement material in a lithium ion battery is basically the same as that in Example 12, except that the single-phase, gas evolution suppressed manganese-based positive electrode lithium supplement material Li6 (Mn0.8 Ca 0.1 Al 0.1 )O4 is replaced with the manganese-based positive electrode lithium replenishing material Li6MnO4 of comparative example 1.

[0154] The manganese-based positive electrode lithium supplement material has a first-cycle charging capacity of 240mAh / g, a discharge capacity of 18mAh / g, a coulombic efficiency of 7.5%, and an oxygen release of 0.8mL / g at a charging cut-off voltage of 4.3V. The addition of 8wt% can compensate for the 11.6% lithium loss of the silicon-based negative electrode; the capacity retention rate of the lithium-ion full battery after 300 cycles is 80%.

[0155] like Figure 5 As shown, by comparing Comparative Example 2 with Example 12, it can be found that the charge capacity of Li6MnO4 in Comparative Example 2 is significantly smaller than that in Example 1. This is because the single-phase, gas evolution suppressed manganese-based positive lithium supplement material prepared in Comparative Example 1 has non-conductive impurity phases of Li2O and MnO ( Figure 1 medium (a)), and the particle size is large (3~15μm, Figure 3 In (a), the poor conductivity cannot promote the transfer of charge and the release of lithium ions, which increases its decomposition voltage and thus cannot release a higher specific capacity within a lower charge cut-off voltage; while the single-phase, gas evolution suppressed manganese-based positive electrode lithium supplement material prepared in Example 1 has a particle size of only 1~4μm, which effectively shortens the transmission distance of ions and electrons and increases the lattice defects of the manganese-based positive electrode lithium supplement material by multi-element doping, which is beneficial to improve Li + Due to the diffusion rate within the material and the electrical conductivity of the particles, the single-phase, gas evolution suppressed manganese-based positive electrode lithium supplement material in Example 1 has a high charge capacity (720 mAh / g).

[0156] Example 13

[0157] The application of a single-phase, gassing-inhibited manganese-based cathode lithium supplement material in a lithium-ion battery comprises the following specific steps:

[0158] (1) Preparation of manganese-based positive electrode lithium supplement material pole piece: the manganese-based positive electrode lithium supplement material Li 5.2 (Mn 0.7 Ti 0.1 Nb 0.2 )O4, conductive additives and polyvinylidene fluoride binder are uniformly dispersed in solvent N-methylpyrrolidone to form a slurry, and the slurry is coated on aluminum foil and dried to obtain a pole piece of manganese-based positive electrode lithium supplement material.

[0159] (2) Test of the charge and discharge specific capacity of manganese-based positive electrode lithium replenishing materials: The electrode and lithium sheet of the manganese-based positive electrode lithium replenishing material are assembled into a half-cell, and then placed on a shelf in a constant temperature chamber at 25°C for 6 hours, and then charged to 4.3V at a constant current of 0.03C (1C=550mAh / g), and then discharged to 3V at 0.05C, and then tested using the Wuhan Blue Electric CT2001A system; the measured charge and discharge specific capacity of the half-cell is the charge and discharge specific capacity of the manganese-based positive electrode lithium replenishing material.

[0160] (3) Preparation of positive electrode manganese-based lithium-supplementing material composite electrode: the positive electrode material (LiNi 0.83 Co 0.12 Mn 0.05 O2), the manganese-based positive electrode lithium replenishing material of Example 2, the conductive additive and the binder are placed in an NMP solvent in a mass ratio of 87:3:5:5 and mixed, wherein the mass fraction of NMP is 50wt%, to form a uniformly dispersed slurry; then, the slurry is coated on aluminum foil, and after drying, a positive electrode manganese-based lithium replenishing material composite electrode sheet is obtained.

[0161] (4) Preparation of negative electrode sheets: The negative electrode material, conductive additive, and lithium polyacrylate binder were mixed in deionized water at a mass ratio of 90:5:5, where the mass fraction of deionized water was 50 wt%, to form a uniform slurry; then, the slurry was coated on the surface of copper foil and dried to obtain the negative electrode sheet.

[0162] (5) Assembly of the full battery: The positive electrode manganese-based lithium supplement material composite electrode is used as the positive electrode, the negative electrode is used as the negative electrode, the positive and negative electrode capacity ratio is 1:1.2, Celgard2050 is selected as the separator, the electrolyte model selected is LB-008 from Duoduo Reagent Company, the electrolyte addition amount is 40µl, and the full battery is assembled.

[0163] The single-phase, gas evolution-inhibited manganese-based positive electrode lithium supplement material has a first-cycle charge capacity of 810mAh / g, a discharge capacity of 22mAh / g, a coulombic efficiency of 2.7%, and an oxygen release of 0.8mL / g at a charge cut-off voltage of 4.3V. An addition of 3wt% can compensate for the 14.7% lithium loss of the silicon-based negative electrode; the capacity retention rate of the lithium-ion full battery after 300 cycles is 94%.

[0164] Example 14

[0165] The application of a single-phase, gassing-inhibited manganese-based cathode lithium supplement material in a lithium-ion battery comprises the following specific steps:

[0166] (1) Preparation of manganese-based positive electrode lithium supplement material pole piece: The manganese-based positive electrode lithium supplement material Li5 (Mn 0.6 Ni 0.2 Zr 0.2)O4, conductive additives and polyvinylidene fluoride binder are uniformly dispersed in solvent N-methylpyrrolidone to form a slurry, and the slurry is coated on aluminum foil and dried to obtain a pole piece of manganese-based positive electrode lithium supplement material.

[0167] (2) Test of the charge and discharge specific capacity of manganese-based positive electrode lithium replenishing materials: The electrode and lithium sheet of the manganese-based positive electrode lithium replenishing material are assembled into a half-cell, and then placed on a shelf in a constant temperature chamber at 25°C for 6 hours, and then charged to 4.3V at a constant current of 0.03C (1C=550mAh / g), and then discharged to 3V at 0.05C, and then tested using the Wuhan Blue Electric CT2001A system; the measured charge and discharge specific capacity of the half-cell is the charge and discharge specific capacity of the manganese-based positive electrode lithium replenishing material.

[0168] (3) Preparation of positive electrode manganese-based lithium-supplementing material composite electrode: the positive electrode material (LiNi 0.83 Co 0.12 Mn 0.05 O2), the manganese-based positive electrode lithium replenishing material of Example 3, the conductive additive and the binder are placed in an NMP solvent in a mass ratio of 85:5:5:5 and mixed, wherein the mass fraction of NMP is 50wt%, to form a uniformly dispersed slurry; then, the slurry is coated on aluminum foil, and after drying, a positive electrode manganese-based lithium replenishing material composite electrode sheet is obtained.

[0169] (4) Preparation of negative electrode sheets: The negative electrode material, conductive additive, and lithium polyacrylate binder were mixed in deionized water at a mass ratio of 90:5:5, where the mass fraction of deionized water was 50 wt%, to form a uniform slurry; then, the slurry was coated on the surface of copper foil and dried to obtain the negative electrode sheet.

[0170] (5) Assembly of the full battery: The positive electrode manganese-based lithium supplement material composite electrode is used as the positive electrode, the negative electrode is used as the negative electrode, the positive and negative electrode capacity ratio is 1:1.2, Celgard2050 is selected as the separator, the electrolyte model selected is LB-008 from Duoduo Reagent Company, the electrolyte addition amount is 40µl, and the full battery is assembled.

[0171] The single-phase, gas evolution-inhibited manganese-based positive electrode lithium supplement material has a first-cycle charge capacity of 773mAh / g, a discharge capacity of 21mAh / g, a coulombic efficiency of 2.7%, and an oxygen release of 0.7mL / g at a charge cut-off voltage of 4.3V. An addition of 5wt% can compensate for the 23.2% lithium loss of the silicon-based negative electrode; the capacity retention rate of the lithium-ion full battery after 300 cycles is 97%.

[0172] Example 15

[0173] The application of a single-phase, gassing-inhibited manganese-based cathode lithium supplement material in a lithium-ion battery comprises the following specific steps:

[0174] (1) Preparation of manganese-based positive electrode lithium supplement material pole piece: The manganese-based positive electrode lithium supplement material Li3 (Mn 0.9 Sn 0.05 Si 0.05 )O4, conductive additives and polyvinylidene fluoride binder are uniformly dispersed in solvent N-methylpyrrolidone to form a slurry, and the slurry is coated on aluminum foil and dried to obtain a pole piece of manganese-based positive electrode lithium supplement material.

[0175] (2) Test of the charge and discharge specific capacity of manganese-based positive electrode lithium replenishing materials: The electrode and lithium sheet of the manganese-based positive electrode lithium replenishing material are assembled into a half-cell, and then placed on a shelf in a constant temperature chamber at 25°C for 6 hours, and then charged to 4.3V at a constant current of 0.03C (1C=550mAh / g), and then discharged to 3V at 0.05C, and then tested using the Wuhan Blue Electric CT2001A system; the measured charge and discharge specific capacity of the half-cell is the charge and discharge specific capacity of the manganese-based positive electrode lithium replenishing material.

[0176] (3) Preparation of positive electrode manganese-based lithium-supplementing material composite electrode: the positive electrode material (LiNi 0.83 Co 0.12 Mn 0.05 O2), the manganese-based positive electrode lithium replenishing material of Example 4, the conductive additive and the binder are placed in an NMP solvent in a mass ratio of 88:2:5:5 and mixed, wherein the mass fraction of NMP is 50wt%, to form a uniformly dispersed slurry; then, the slurry is coated on aluminum foil, and after drying, a positive electrode manganese-based lithium replenishing material composite electrode sheet is obtained.

[0177] (4) Preparation of negative electrode sheets: The negative electrode material, conductive additive, and lithium polyacrylate binder were mixed in deionized water at a mass ratio of 90:5:5, where the mass fraction of deionized water was 50 wt%, to form a uniform slurry; then, the slurry was coated on the surface of copper foil and dried to obtain the negative electrode sheet.

[0178] (5) Assembly of the full battery: The positive electrode manganese-based lithium supplement material composite electrode is used as the positive electrode, the negative electrode is used as the negative electrode, the positive and negative electrode capacity ratio is 1:1.2, Celgard2050 is selected as the separator, the electrolyte model selected is LB-008 from Duoduo Reagent Company, the electrolyte addition amount is 40µl, and the full battery is assembled.

[0179] The single-phase, gas evolution-inhibited manganese-based positive electrode lithium supplement material has a first-cycle charge capacity of 920mAh / g, a discharge capacity of 30mAh / g, a coulombic efficiency of 3.2%, and an oxygen release of 1.2mL / g at a charge cut-off voltage of 4.3V. An addition of 2wt% can compensate for the 11.1% lithium loss of the silicon-based negative electrode; the capacity retention rate of the lithium-ion full battery after 300 cycles is 92%.

[0180] Example 16

[0181] The application of a single-phase, gassing-inhibited manganese-based cathode lithium supplement material in a lithium-ion battery comprises the following specific steps:

[0182] (1) Preparation of manganese-based positive electrode lithium supplement material pole piece: The manganese-based positive electrode lithium supplement material Li2 (Mn 0.5 Co 0.3 Fe 0.2 )O4, conductive additives and polyvinylidene fluoride binder are uniformly dispersed in solvent N-methylpyrrolidone to form a slurry, and the slurry is coated on aluminum foil and dried to obtain a pole piece of manganese-based positive electrode lithium supplement material.

[0183] (2) Test of the charge and discharge specific capacity of manganese-based positive electrode lithium replenishing materials: The electrode and lithium sheet of the manganese-based positive electrode lithium replenishing material are assembled into a half-cell, and then placed on a shelf in a constant temperature chamber at 25°C for 6 hours, and then charged to 4.3V at a constant current of 0.03C (1C=550mAh / g), and then discharged to 3V at 0.05C, and then tested using the Wuhan Blue Electric CT2001A system; the measured charge and discharge specific capacity of the half-cell is the charge and discharge specific capacity of the manganese-based positive electrode lithium replenishing material.

[0184] (3) Preparation of positive electrode manganese-based lithium-supplementing material composite electrode: the positive electrode material (LiNi 0.83 Co 0.12 Mn 0.05 O2), the manganese-based positive electrode lithium replenishing material of Example 5, the conductive additive and the binder are placed in an NMP solvent in a mass ratio of 80:10:5:5 and mixed, wherein the mass fraction of NMP is 50wt%, to form a uniformly dispersed slurry; then, the slurry is coated on aluminum foil, and after drying, a positive electrode manganese-based lithium replenishing material composite electrode sheet is obtained.

[0185] (4) Preparation of negative electrode sheets: The negative electrode material, conductive additive, and lithium polyacrylate binder were mixed in deionized water at a mass ratio of 90:5:5, where the mass fraction of deionized water was 50 wt%, to form a uniform slurry; then, the slurry was coated on the surface of copper foil and dried to obtain the negative electrode sheet.

[0186] (5) Assembly of the full battery: The positive electrode manganese-based lithium supplement material composite electrode is used as the positive electrode, the negative electrode is used as the negative electrode, the positive and negative electrode capacity ratio is 1:1.2, Celgard2050 is selected as the separator, the electrolyte model selected is LB-008 from Duoduo Reagent Company, the electrolyte addition amount is 40µl, and the full battery is assembled.

[0187] The single-phase, gas evolution-inhibited manganese-based positive electrode lithium supplement material has a first-cycle charge capacity of 650mAh / g, a discharge capacity of 16mAh / g, a coulombic efficiency of 2.4%, and an oxygen release of 0.6mL / g at a charge cut-off voltage of 4.3V. An addition of 10wt% can compensate for 39.4% of the lithium loss of the silicon-based negative electrode; the capacity retention rate of the lithium-ion full battery after 300 cycles is 99%.

[0188] Example 17

[0189] The application of a single-phase, gassing-inhibited manganese-based cathode lithium supplement material in a lithium-ion battery comprises the following specific steps:

[0190] (1) Preparation of manganese-based positive electrode lithium supplement material pole piece: The manganese-based positive electrode lithium supplement material Li6 (Mn 0.05 K 0.45 B 0.5 )O4, conductive additives and polyvinylidene fluoride binder are uniformly dispersed in solvent N-methylpyrrolidone to form a slurry, and the slurry is coated on aluminum foil and dried to obtain a pole piece of manganese-based positive electrode lithium supplement material.

[0191] (2) Test of the charge and discharge specific capacity of manganese-based positive electrode lithium replenishing materials: The electrode and lithium sheet of the manganese-based positive electrode lithium replenishing material are assembled into a half-cell, and then placed on a shelf in a constant temperature chamber at 25°C for 6 hours, and then charged to 4.3V at a constant current of 0.03C (1C=550mAh / g), and then discharged to 3V at 0.05C, and then tested using the Wuhan Blue Electric CT2001A system; the measured charge and discharge specific capacity of the half-cell is the charge and discharge specific capacity of the manganese-based positive electrode lithium replenishing material.

[0192] (3) Preparation of positive electrode manganese-based lithium-supplementing material composite electrode: the positive electrode material (LiNi 0.83 Co 0.12 Mn 0.05 O2), the manganese-based positive electrode lithium replenishing material of Example 6, the conductive additive and the binder are placed in an NMP solvent in a mass ratio of 87:3:5:5 and mixed, wherein the mass fraction of NMP is 50wt%, to form a uniformly dispersed slurry; then, the slurry is coated on aluminum foil, and after drying, a positive electrode manganese-based lithium replenishing material composite electrode sheet is obtained.

[0193] (4) Preparation of negative electrode sheets: The negative electrode material, conductive additive, and lithium polyacrylate binder were mixed in deionized water at a mass ratio of 90:5:5, where the mass fraction of deionized water was 50 wt%, to form a uniform slurry; then, the slurry was coated on the surface of copper foil and dried to obtain the negative electrode sheet.

[0194] (5) Assembly of the full battery: The positive electrode manganese-based lithium supplement material composite electrode is used as the positive electrode, the negative electrode is used as the negative electrode, the positive and negative electrode capacity ratio is 1:1.2, Celgard2050 is selected as the separator, the electrolyte model selected is LB-008 from Duoduo Reagent Company, the electrolyte addition amount is 40µl, and the full battery is assembled.

[0195] The single-phase, gas evolution-inhibited manganese-based positive electrode lithium supplement material has a first-cycle charge capacity of 550mAh / g, a discharge capacity of 12mAh / g, a coulombic efficiency of 2.2%, and an oxygen release of 0.4mL / g at a charge cut-off voltage of 4.3V. An addition of 3wt% can compensate for 10% of the lithium loss of the silicon-based negative electrode; the capacity retention rate of the lithium-ion full battery after 300 cycles is 85%.

[0196] Example 18

[0197] The application of a single-phase, gassing-inhibited manganese-based cathode lithium supplement material in a lithium-ion battery comprises the following specific steps:

[0198] (1) Preparation of manganese-based positive electrode lithium supplement material pole piece: the manganese-based positive electrode lithium supplement material Li 3.5 (Mn 0.75 Mg 0.15 Si 0.1 )O4, conductive additives and polyvinylidene fluoride binder are uniformly dispersed in solvent N-methylpyrrolidone to form a slurry, and the slurry is coated on aluminum foil and dried to obtain a pole piece of manganese-based positive electrode lithium supplement material.

[0199] (2) Test of the charge and discharge specific capacity of manganese-based positive electrode lithium replenishing materials: The electrode and lithium sheet of the manganese-based positive electrode lithium replenishing material are assembled into a half-cell, and then placed on a shelf in a constant temperature chamber at 25°C for 6 hours, and then charged to 4.3V at a constant current of 0.03C (1C=550mAh / g), and then discharged to 3V at 0.05C, and then tested using the Wuhan Blue Electric CT2001A system; the measured charge and discharge specific capacity of the half-cell is the charge and discharge specific capacity of the manganese-based positive electrode lithium replenishing material.

[0200] (3) Preparation of positive electrode manganese-based lithium-supplementing material composite electrode: the positive electrode material (LiNi 0.83 Co 0.12 Mn 0.05 O2), the manganese-based positive electrode lithium replenishing material of Example 7, the conductive additive and the binder are placed in an NMP solvent in a mass ratio of 87:3:5:5 and mixed, wherein the mass fraction of NMP is 50wt%, to form a uniformly dispersed slurry; then, the slurry is coated on an aluminum foil, and after drying, a positive electrode manganese-based lithium replenishing material composite electrode sheet is obtained.

[0201] (4) Preparation of negative electrode sheets: The negative electrode material, conductive additive, and lithium polyacrylate binder were mixed in deionized water at a mass ratio of 90:5:5, where the mass fraction of deionized water was 50 wt%, to form a uniform slurry; then, the slurry was coated on the surface of copper foil and dried to obtain the negative electrode sheet.

[0202] (5) Assembly of the full battery: The positive electrode manganese-based lithium supplement material composite electrode is used as the positive electrode, the negative electrode is used as the negative electrode, the positive and negative electrode capacity ratio is 1:1.2, Celgard2050 is selected as the separator, the electrolyte model selected is LB-008 from Duoduo Reagent Company, the electrolyte addition amount is 40µl, and the full battery is assembled.

[0203] The single-phase, gas evolution-inhibited manganese-based positive electrode lithium supplement material has a first-cycle charge capacity of 600mAh / g, a discharge capacity of 14mAh / g, a coulombic efficiency of 2.3%, and an oxygen release of 0.5mL / g at a charge cut-off voltage of 4.3V. An addition of 4wt% can compensate for the 14% lithium loss of the silicon-based negative electrode; the capacity retention rate of the lithium-ion full battery after 300 cycles is 89%.

[0204] Example 19

[0205] The application of a single-phase, gassing-inhibited manganese-based cathode lithium supplement material in a lithium-ion battery comprises the following specific steps:

[0206] (1) Preparation of manganese-based positive electrode lithium supplement material pole piece: the manganese-based positive electrode lithium supplement material Li 4.8 (Mn 0.65 V 0.2 B 0.15 )O4, conductive additives and polyvinylidene fluoride binder are uniformly dispersed in solvent N-methylpyrrolidone to form a slurry, and the slurry is coated on aluminum foil and dried to obtain a pole piece of manganese-based positive electrode lithium supplement material.

[0207] (2) Test of the charge and discharge specific capacity of manganese-based positive electrode lithium replenishing materials: The electrode and lithium sheet of the manganese-based positive electrode lithium replenishing material are assembled into a half-cell, and then placed on a shelf in a constant temperature chamber at 25°C for 6 hours, and then charged to 4.3V at a constant current of 0.03C (1C=550mAh / g), and then discharged to 3V at 0.05C, and then tested using the Wuhan Blue Electric CT2001A system; the measured charge and discharge specific capacity of the half-cell is the charge and discharge specific capacity of the manganese-based positive electrode lithium replenishing material.

[0208] (3) Preparation of positive electrode manganese-based lithium-supplementing material composite electrode: the positive electrode material (LiNi 0.83 Co 0.12 Mn 0.05O2), the manganese-based positive electrode lithium replenishing material of Example 8, the conductive additive and the binder are placed in an NMP solvent in a mass ratio of 87:3:5:5 and mixed, wherein the mass fraction of NMP is 50wt%, to form a uniformly dispersed slurry; then, the slurry is coated on aluminum foil, and after drying, a positive electrode manganese-based lithium replenishing material composite electrode sheet is obtained.

[0209] (4) Preparation of negative electrode sheets: The negative electrode material, conductive additive, and lithium polyacrylate binder were mixed in deionized water at a mass ratio of 90:5:5, where the mass fraction of deionized water was 50 wt%, to form a uniform slurry; then, the slurry was coated on the surface of copper foil and dried to obtain the negative electrode sheet.

[0210] (5) Assembly of the full battery: The positive electrode manganese-based lithium supplement material composite electrode is used as the positive electrode, the negative electrode is used as the negative electrode, the positive and negative electrode capacity ratio is 1:1.2, Celgard2050 is selected as the separator, the electrolyte model selected is LB-008 from Duoduo Reagent Company, the electrolyte addition amount is 40µl, and the full battery is assembled.

[0211] The single-phase, gas evolution-inhibited manganese-based positive electrode lithium supplement material has a first-cycle charge capacity of 650mAh / g, a discharge capacity of 15mAh / g, a coulombic efficiency of 2.3%, and an oxygen release of 0.6mL / g at a charge cut-off voltage of 4.3V. An addition of 5wt% can compensate for 20% of the lithium loss of the silicon-based negative electrode; the capacity retention rate of the lithium-ion full battery after 300 cycles is 91%.

[0212] Example 20

[0213] The application of a single-phase, gassing-inhibited manganese-based cathode lithium supplement material in a lithium-ion battery comprises the following specific steps:

[0214] (1) Preparation of manganese-based positive electrode lithium supplement material pole piece: the manganese-based positive electrode lithium supplement material Li 2.8 (Mn 0.55 Cu 0.3 Zn 0.15 )O4, conductive additives and polyvinylidene fluoride binder are uniformly dispersed in solvent N-methylpyrrolidone to form a slurry, and the slurry is coated on aluminum foil and dried to obtain a pole piece of manganese-based positive electrode lithium supplement material.

[0215] (2) Test of the charge and discharge specific capacity of manganese-based positive electrode lithium replenishing materials: The electrode and lithium sheet of the manganese-based positive electrode lithium replenishing material are assembled into a half-cell, and then placed on a shelf in a constant temperature chamber at 25°C for 6 hours, and then charged to 4.3V at a constant current of 0.03C (1C=550mAh / g), and then discharged to 3V at 0.05C, and then tested using the Wuhan Blue Electric CT2001A system; the measured charge and discharge specific capacity of the half-cell is the charge and discharge specific capacity of the manganese-based positive electrode lithium replenishing material.

[0216] (3) Preparation of positive electrode manganese-based lithium-supplementing material composite electrode: the positive electrode material (LiNi 0.83 Co 0.12 Mn 0.05 O2), the manganese-based positive electrode lithium replenishing material of Example 8, the conductive additive and the binder are placed in an NMP solvent in a mass ratio of 87:3:5:5 and mixed, wherein the mass fraction of NMP is 50wt%, to form a uniformly dispersed slurry; then, the slurry is coated on aluminum foil, and after drying, a positive electrode manganese-based lithium replenishing material composite electrode sheet is obtained.

[0217] (4) Preparation of negative electrode sheets: The negative electrode material, conductive additive, and lithium polyacrylate binder were mixed in deionized water at a mass ratio of 90:5:5, where the mass fraction of deionized water was 50 wt%, to form a uniform slurry; then, the slurry was coated on the surface of copper foil and dried to obtain the negative electrode sheet.

[0218] (5) Assembly of the full battery: The positive electrode manganese-based lithium supplement material composite electrode is used as the positive electrode, the negative electrode is used as the negative electrode, the positive and negative electrode capacity ratio is 1:1.2, Celgard2050 is selected as the separator, the electrolyte model selected is LB-008 from Duoduo Reagent Company, the electrolyte addition amount is 40µl, and the full battery is assembled.

[0219] The single-phase, gassing-inhibited manganese-based positive electrode lithium supplement material has a first-cycle charge capacity of 620mAh / g, a discharge capacity of 14mAh / g, a coulombic efficiency of 2.2%, and an oxygen release of 0.4mL / g at a charge cut-off voltage of 4.3V. An addition of 5wt% can compensate for 18% of the lithium loss of the silicon-based negative electrode; the capacity retention rate of the lithium-ion full battery after 300 cycles is 90%.

[0220] Example 21

[0221] The application of a single-phase, gassing-inhibited manganese-based cathode lithium supplement material in a lithium-ion battery comprises the following specific steps:

[0222] (1) Preparation of manganese-based positive electrode lithium supplement material pole piece: the manganese-based positive electrode lithium supplement material Li 5.2 (Mn 0.5 Cr 0.25 Si 0.25 )O4, conductive additives and polyvinylidene fluoride binder are uniformly dispersed in solvent N-methylpyrrolidone to form a slurry, and the slurry is coated on aluminum foil and dried to obtain a pole piece of manganese-based positive electrode lithium supplement material.

[0223] (2) Test of the charge and discharge specific capacity of manganese-based positive electrode lithium replenishing materials: The electrode and lithium sheet of the manganese-based positive electrode lithium replenishing material are assembled into a half-cell, and then placed on a shelf in a constant temperature chamber at 25°C for 6 hours, and then charged to 4.3V at a constant current of 0.03C (1C=550mAh / g), and then discharged to 3V at 0.05C, and then tested using the Wuhan Blue Electric CT2001A system; the measured charge and discharge specific capacity of the half-cell is the charge and discharge specific capacity of the manganese-based positive electrode lithium replenishing material.

[0224] (3) Preparation of positive electrode manganese-based lithium-supplementing material composite electrode: the positive electrode material (LiNi 0.83 Co 0.12 Mn 0.05 O2), the manganese-based positive electrode lithium replenishing material of Example 10, the conductive additive and the binder are placed in an NMP solvent in a mass ratio of 87:3:5:5 and mixed, wherein the mass fraction of NMP is 50wt%, to form a uniformly dispersed slurry; then, the slurry is coated on an aluminum foil, and after drying, a positive electrode manganese-based lithium replenishing material composite electrode sheet is obtained.

[0225] (4) Preparation of negative electrode sheets: The negative electrode material, conductive additive, and lithium polyacrylate binder were mixed in deionized water at a mass ratio of 90:5:5, where the mass fraction of deionized water was 50 wt%, to form a uniform slurry; then, the slurry was coated on the surface of copper foil and dried to obtain the negative electrode sheet.

[0226] (5) Assembly of the full battery: The positive electrode manganese-based lithium supplement material composite electrode is used as the positive electrode, the negative electrode is used as the negative electrode, the positive and negative electrode capacity ratio is 1:1.2, Celgard2050 is selected as the separator, the electrolyte model selected is LB-008 from Duoduo Reagent Company, the electrolyte addition amount is 40µl, and the full battery is assembled.

[0227] The single-phase, gas evolution-inhibited manganese-based positive electrode lithium supplement material has a first-cycle charge capacity of 860mAh / g, a discharge capacity of 18mAh / g, a coulombic efficiency of 2.1%, and an oxygen release of 0.6mL / g at a charge cut-off voltage of 4.3V. An addition of 6wt% can compensate for 31% of the lithium loss of the silicon-based negative electrode; the capacity retention rate of the lithium-ion full battery after 300 cycles is 97%.

[0228] Example 22

[0229] The application of a single-phase, gassing-inhibited manganese-based cathode lithium supplement material in a lithium-ion battery comprises the following specific steps:

[0230] (1) Preparation of manganese-based positive electrode lithium supplement material pole piece: The manganese-based positive electrode lithium supplement material Li6 (Mn 0.1 K 0.45 B 0.45)O4, conductive additives and polyvinylidene fluoride binder are uniformly dispersed in solvent N-methylpyrrolidone to form a slurry, and the slurry is coated on aluminum foil and dried to obtain a pole piece of manganese-based positive electrode lithium supplement material.

[0231] (2) Test of the charge and discharge specific capacity of manganese-based positive electrode lithium replenishing materials: The electrode and lithium sheet of the manganese-based positive electrode lithium replenishing material are assembled into a half-cell, and then placed on a shelf in a constant temperature chamber at 25°C for 6 hours, and then charged to 4.3V at a constant current of 0.03C (1C=550mAh / g), and then discharged to 3V at 0.05C, and then tested using the Wuhan Blue Electric CT2001A system; the measured charge and discharge specific capacity of the half-cell is the charge and discharge specific capacity of the manganese-based positive electrode lithium replenishing material.

[0232] (3) Preparation of positive electrode manganese-based lithium-supplementing material composite electrode: the positive electrode material (LiNi 0.83 Co 0.12 Mn 0.05 O2), the manganese-based positive electrode lithium replenishing material of Example 11, the conductive additive and the binder are placed in an NMP solvent in a mass ratio of 87:3:5:5 and mixed, wherein the mass fraction of NMP is 50wt%, to form a uniformly dispersed slurry; then, the slurry is coated on an aluminum foil, and after drying, a positive electrode manganese-based lithium replenishing material composite electrode sheet is obtained.

[0233] (4) Preparation of negative electrode sheets: The negative electrode material, conductive additive, and lithium polyacrylate binder were mixed in deionized water at a mass ratio of 90:5:5, where the mass fraction of deionized water was 50 wt%, to form a uniform slurry; then, the slurry was coated on the surface of copper foil and dried to obtain the negative electrode sheet.

[0234] (5) Assembly of the full battery: The positive electrode manganese-based lithium supplement material composite electrode is used as the positive electrode, the negative electrode is used as the negative electrode, the positive and negative electrode capacity ratio is 1:1.2, Celgard2050 is selected as the separator, the electrolyte model selected is LB-008 from Duoduo Reagent Company, the electrolyte addition amount is 40µl, and the full battery is assembled.

[0235] The single-phase, gas evolution-inhibited manganese-based positive electrode lithium supplement material has a first-cycle charge capacity of 905mAh / g, a discharge capacity of 6.3mAh / g, a coulombic efficiency of 0.7%, and an oxygen release of 0.5mL / g at a charge cut-off voltage of 4.3V. An addition of 4wt% can compensate for the 22% lithium loss of the silicon-based negative electrode; the capacity retention rate of the lithium-ion full battery after 300 cycles is 95%.

Claims

1. A single-phase, gassing-suppressed manganese-based cathode lithium supplement material, characterized by: The chemical formula is Li x (Mn y M1 a M2 b )O4, wherein 2≤x≤6, 0.05≤y≤1, 0.01≤a≤0.94, 0.01≤b≤0.94, M1 is selected from at least one of K, Ca, Mg, Sn, Ti, Ni, V, Cr, Co, and Cu, and M2 is selected from at least one of Zr, Al, Nb, Mo, Fe, B, Si, and Zn; 0.02≤a+b≤0.95, and y+a+b≤1; The single-phase, gassing-inhibited manganese-based cathode lithium supplement material is prepared by uniformly spreading a precursor powder obtained by mixing lithium source, manganese source and other metal / non-metal source spheroidal graphite in an alumina crucible, calcining it in a tube furnace, and cooling it to obtain the single-phase, gassing-inhibited manganese-based cathode lithium supplement material. The calcination conditions are as follows: calcination temperature of 500-1000°C, heating rate of 1-10°C / min, calcination time of 10-24h, calcination atmosphere of nitrogen or argon, and cooling after calcination; cooling conditions are as follows: in a nitrogen or argon atmosphere, slowly cooling to 30°C at a cooling rate of 1-5°C / min, and maintaining for 2-10 hours.

2. The method for preparing a single-phase, gassing-suppressed manganese-based positive electrode lithium supplement material according to claim 1, characterized in that The steps include: Step S1: weighing a lithium source, a manganese source, and other metal / non-metal sources according to the molar ratio of each element in the chemical formula, and ball-milling and mixing them to obtain a precursor powder; Step S2: evenly spread the precursor powder of step S1 in an alumina crucible, place it in a tube furnace for calcination, and obtain a single-phase, gas evolution-inhibited manganese-based positive electrode lithium supplement material after cooling.

3. The method for preparing a single-phase, gassing-suppressed manganese-based positive electrode lithium supplement material according to claim 2, characterized in that: In step S1 , the lithium source is one or more of lithium peroxide, lithium oxalate, lithium oxide, lithium hydroxide, lithium sulfate, lithium nitrate, lithium carbonate and lithium acetate, and the manganese source is one or more of manganese oxide and manganese hydroxide.

4. The method for preparing a single-phase, gassing-suppressed manganese-based positive electrode lithium supplement material according to claim 2, characterized in that: In step S1, the other metal / non-metal sources include: a potassium source of one or more of potassium oxide, potassium superoxide and potassium hydroxide; a calcium source of one or more of calcium oxide, calcium peroxide and calcium hydroxide; a magnesium source of one or more of magnesium oxide, magnesium peroxide and magnesium hydroxide; a tin source of one or more of tin dioxide, stannous oxide and tin hydroxide; a titanium source of one or more of titanium dioxide and titanium hydroxide; a vanadium source of one or more of vanadium pentoxide and vanadium hydroxide; a cobalt source of one or more of cobalt oxide, cobalt hydroxide and cobalt trioxide; a chromium source of one or more of chromium trioxide and chromium hydroxide; a nickel source of one or more of chromium oxide and chromium hydroxide; The present invention relates to a novel nanostructured carbonic acid ...

5. The method for preparing a single-phase, gassing-suppressed manganese-based positive lithium supplement material according to claim 2, characterized in that: In step S1, the ball milling mixing speed is 200-1000 rpm, the time is 1-20 hours, the ball milling beads are zirconium beads, and the ball-to-material ratio is 10-25:

1.

6. The method for preparing a single-phase, gassing-suppressed manganese-based positive electrode lithium supplement material according to claim 2, characterized in that: In step S2, the calcination conditions are: calcination temperature of 500-1000°C, heating rate of 1-10°C / min, calcination time of 10-24h, calcination atmosphere of nitrogen or argon, and cooling after calcination.

7. The method for preparing a single-phase, gassing-suppressed manganese-based positive electrode lithium supplement material according to claim 2, characterized in that: The cooling conditions in step S2 are: slowly cooling to 30° C. at a cooling rate of 1 to 5° C. / min under a nitrogen or argon atmosphere, and maintaining the temperature for 2 to 10 hours.

8. Use of a single-phase, gassing-suppressed manganese-based cathode lithium supplement material in a lithium-ion battery according to claim 1, characterized in that: The single-phase, gas evolution-inhibited manganese-based positive electrode lithium replenishing material has a first-cycle charge capacity ≥550mAh / g, a discharge capacity ≤30mAh / g, a coulombic efficiency of 0.7-8.5%, and an oxygen release amount ≤1.2mL / g at a charge cut-off voltage of 4.3V. An addition amount of 2-10wt% can compensate for 10-40% of the lithium loss of the silicon-based negative electrode.

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